Pesticidal 4-halogeno-5-nitrothiazoles

ABSTRACT

Fungicidal 4-halogeno-5-nitrothiazoles of the formula ##STR1## in which Hal represents halogen, 
     A represents O, S, SO, SO 2  or N--R 1 , wherein 
     R and R 1  each independently is hydrogen or an organic radical, or together with 
     N form a heterocyclic ring, 
     with the exception that R is not hydrogen if A represents SO or SO 2 . 
     Compounds of the formula ##STR2## in which Hal&#39; and Hal 1&#39;  independently of one another represent chlorine, iodine or fluorine, with the proviso that the two Hals may not simultaneously be chlorine, 
     are also effective in protecting industrial materials against microbes.

This is a division of application Ser. No. 378,894, filed July 12, 1989,now U.S. Pat. No. 4,962,102.

The present invention relates to new 4-halogeno-5-nitrothiazolederivatives, several processes for their preparation and their use asagents for combating pests, and some new intermediate products.

It is known that thiazoles which are substituted, for example, byhydroxyphenoxy are used in medicine for the treatment of tumors (compareWO 88/00,944).

It is furthermore known that 2,4-dichloro-5-nitrothiazole has amicrobicidal action, above all a fungicidal action, in plant protection(compare DE-OS (German Published Specification) 3,518,520).

Thiazole derivatives, such as, for example,4,5-dichloro-2-propinyloxy-thiazole, are also known as synergists(compare DE-OS (German Published Specification) 3,030,661).

It is furthermore known that certain substituted thiazoles, such as, forexample, 4-benzimidazol-2-yl-thiazole (thiabendazol), are used asfungicides for the protection of materials (cf., for example, R. Wegler"Chemie der Pflanzenschutz- und Schadlingsbekampfungsmittel" [Chemistryof Plant Protection Agents and Pesticides], Vol. 2, p. 124, and Vol. 3,p. 292; Springer Verlag, Berlin, Heidelberg, N.Y. 1970).

However, the range of action of these previously known compounds hassome gaps and their microbicidal activity is not always satisfactory incertain areas of indication.

New 4-halogeno-5-nitrothiazole derivatives of the formula (I) ##STR3##in which Hal represents halogen,

A represents O, S, SO, SO₂ or N--R¹, wherein

R¹ represents hydrogen, alkyl, alkenyl, halogenoalkyl or cyanoalkyl, orrepresents cycloalkyl, aryl or aralkyl, in each case optionallysubstituted by one or more identical or different substituents, and

R represents hydrogen, alkyl, alkenyl or alkinyl, it being possible forthe abovementioned radicals in each case to be optionally substituted byone or more identical or different substituents from the groupcomprising halogen, alkoxy, aryloxy, alkylmercapto, arylmercapto andcyano, or represents cycloalkyl which is optionally substituted by oneor more identical or different alkyl substituents, it being possible fora ring to be fused on in addition to the alkyl substitution, orrepresents aralkyl which is optionally substituted in the aryl part byone or more identical or different substituents from the groupcomprising halogen, alkyl, halogenoalkyl, nitro, alkoxy, alkylmercaptoand cyano, or represents aryl which is optionally substituted by one ormore identical or different substituents from the group comprisinghalogen, alkyl, alkenyl, alkinyl, halogenoalkyl, nitro, alkoxy,alkylmercapto, dialkylamino, carbalkoxy, carbamoyl, N-alkylcarbamoyl,N,N-dialkylcarbamoyl, halogenoalkyloxy, halogenoalkylmercapto,alkylsulphonylamino, alkylsulphonyl, aryl, aryloxy, arylmercapto,acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl,aralkyloxy, aralkylmercapto, acylamino, acylalkylamino, cycloalkyl andcyano, or

R and R¹, together with the nitrogen atom on which they stand, form aring which can optionally be interrupted by one or more furtheridentical or different hetero atoms and which can optionally besubstituted by one or more identical or different substituents,

with the exception that R is not hydrogen if A represents SO or SO₂,have been found.

It has furthermore been found that the 4-halogeno-5-nitrothiazolederivatives of the formula (I) ##STR4## in which Hal represents halogen,

A represents O, S, SO, SO₂ or N--R¹, wherein

R¹ represents hydrogen, alkyl, alkenyl, halogenoalkyl or cyanoalkyl, orrepresents cycloalkyl, aryl or aralkyl, in each case optionallysubstituted by one or more identical or different substituents, and

represents hydrogen, alkyl, alkenyl or alkinyl, it being possible forthe abovementioned radicals in each case to be optionally substituted byone or more identical or different substituents from the groupcomprising halogen, alkoxy, aryloxy, alkylmercapto, arylmercapto andcyano, or represents cycloalkyl which is optionally substituted by oneor more identical or different alkyl substituents, it being possible fora ring to be fused on in addition to the alkyl substitution, orrepresents aralkyl which is optionally substituted in the aryl part byone or more identical or different substituents from the groupcomprising halogen, alkyl, halogenoalkyl, nitro, alkoxy, alkylmercaptoand cyano, or represents aryl which is optionally substituted by one ormore identical or different substituents from the group comprisinghalogen, alkyl, alkenyl, alkinyl, halogenoalkyl, nitro, alkoxy,alkylmercapto, dialkylamino, carbalkoxy, carbamoyl, N-alkylcarbamoyl,N,N-dialkylcarbamoyl, halogenoalkyloxy, halogenoalkylmercapto,alkylsulphonylamino, alkylsulphonyl, aryl, aryloxy, arylmercapto,acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl,aralkyloxy, aralkylmercapto, acylamino, acylalkylamino, cycloalkyl andcyano, or

R and R¹, together with the nitrogen atom on which they stand, form aring which can optionally be interrupted by one or more furtheridentical or different hetero atoms and which can optionally besubstituted by one or more identical or different substituents,

with the exception that R is not hydrogen if A represents SO or SO₂, areobtained by a process in which

a) in the case where A represents O, S, SO₂ or NR¹,2,4-dihalogeno-5-nitrothiazoles of the formula (II) ##STR5## in whichHal and Hal¹ denote identical or different halogen atoms,

are reacted with nucleophiles of the formula (III)

    H--A'--R                                                   (III)

in which

R has the abovementioned meaning and

A' represents O, S, SO₂ or NR¹, wherein R¹ has the abovementionedmeaning,

or metal salts thereof, if appropriate in the presence of acid-bindingagents and in the presence of diluents,

b) in the case where A--R represents ##STR6##2,4-dihalogeno-5-nitrothiazoles of the formula (II) are reacted withN,N-dimethylarylamines of the formula (IV) ##STR7## in which aryl hasthe meaning given for aryl under R, in the presence of diluents,

c) in the case where A represents SO₂ or SO, 4-halogeno-5-nitrothiazolylsulphides of the formula (V) ##STR8## in which Hal and R have theabovementioned meanings, α) are reacted with at least 2 mols of anoxidizing agent in the presence of a diluent which is inert under thereaction conditions, or

β) are reacted with about 1 mol of an oxidizing agent in the presence ofa diluent which is inert under the reaction conditions.

Finally, it has been found that the new 4-halogeno-5-nitrothiazolederivatives of the formula (I) have a potent action against pests, aboveall against fungi in the plant kingdom and against microbes inindustrial materials.

Suprisingly, the 4-halogeno-5-nitrothiazole derivatives of the formula(I) according to the invention amongst other things exhibit aconsiderably more potent fungicidal activity in plant protection than,for example, the commercial products Captan(N-trichloromethylthio-tetrahydrophthalimide), Euparen(N,N-dimethyl-N'-phenyl-N'-(fluorodichloromethylthio)-sulphamide orCurzate [2-cyano-N-(ethylaminocarbonyl)-2-methoximino)-acetamide], whichare known from the prior art and are closely related compounds from thepoint of view of their action. In addition, they have a bettermicrobicidal action in materials protection than the known4-benaimidazol-2-yl-thiazole.

In the context of the present invention, the substituents have themeanings given, and in general some substituents are listed below.

Halogen can, wherever this is not indicated otherwise, denote fluorine,chlorine, bromine and iodine.

Alkyl here in general in R represents a straight-chain or branchedhydrocarbon radical having 1 to 12 carbon atoms. Examples which may bementioned are methyl, ethyl, propyl, isopropyl, butyl, isobutyl,t-butyl, pentyl, isopentyl, hexyl, isohexyl, heptyl, isoheptyl, octyland isooctyl.

Alkenyl in general in R represents a straight-chain or branchedhydrocarbon radical having 3 to 12 carbon atoms and one or more,preferably one or two, double bonds. Examples which may be mentioned areallyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl,isopentenyl, hexyl, isohexyl, heptenyl, isoheptenyl, octenyl andisooctenyl.

Cycloalkyl in general in R represents a cyclic hydrocarbon radicalhaving 3 to 8 carbon atoms. The cyclopropyl, cyclopentyl or cyclohexylring is preferred. Examples which may be mentioned are cyclopropyl,cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.

Halogenoalkyl in general represents straight-chain or branched loweralkyl having 1 to 8 carbon atoms and one or more halogen atoms. Exampleswhich may be mentioned are: fluoromethyl, chloromethyl, bromomethyl,fluoroethyl, chloroethyl, bromoethyl, fluoropropyl, chloropropyl,bromopropyl, fluorobutyl, chlorobutyl, bromobutyl, fluoroisopropyl,chloroisopropyl, bromoisopropyl, difluoromethyl, trifluoromethyl,dichloromethyl, trichloromethyl, difluoroethyl, dichloroethyl,trifluoroethyl, tetrafluoroethyl, pentafluoroethyl, trichloroethyl andtrifluoropropyl. Trifluoromethyl, difluoromethyl, fluoromethyl,chloromethyl and trifluoroethyl are especially preferred.Halogenoalkenyl in general represents straight-chain or branched alkenylhaving up to 8 carbon atoms, one or more identical or different halogenatoms and one or more double bonds. Radicals with one double bond arepreferred. Examples which may be mentioned are 2,2-dichlorovinyl and1,2,2-trichlorovinyl.

Aryl can represent an aromatic hydrocarbon radical having 6 to 12 carbonatoms. Examples which may be mentioned are phenyl and naphthyl. Phenyland naphthyl are preferred.

Aralkyl can represent a radical having 7 to 16 carbon atoms, it beingpossible for a straight-chain or branched alkyl radical having 1 to 4carbon atoms to be substituted by an aromatic radical having 6 to 12carbon atoms. Examples which may be mentioned are benzyl, phenethyl andphenylpropyl. Benzyl and phenethyl are preferred.

The aryl and aralkyl radicals can optionally be substituted by one ormore identical or different substituents.

Alkoxyalkyl and alkylmercaptoalkyl in general represent a straight-chainor branched hydrocarbon radical which has 1 to 4 carbon atoms per alkylpart and is bonded via oxygen or sulphur. Examples which may bementioned are methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl,ethoxymethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, propoxymethyl,propoxyethyl, propoxypropyl, propoxybutyl, butoxymethyl, butoxyethyl,butoxypropyl and butoxybutyl.

Furthermore methylthiomethyl, methylthioethyl, methylthiopropyl,methylthiobutyl, ethylthiomethyl, ethylthioethyl, ethylthiopropyl,ethylthiobutyl, propylthiomethyl, propylthioethyl, propylthiopropyl,propylthiobutyl, butylthiomethyl, butylthioethyl, butylthiopropyl andbutylthiobutyl.

Formula (I) provides a general definition of the4-halogeno-5-nitrothiazole derivatives according to the invention.Preferred compounds of the formula (I) are those in which

Hal represents fluorine, chlorine, bromine or iodine,

A represents O, S, SO, SO₂ or NR¹, wherein

R¹ represents hydrogen, alkyl having 1 to 4 carbon atoms, alkenyl having3 to 5 carbon atoms or halogenoalkyl having 1 to 3 carbon atoms and 1 to5 identical or different halogen atoms, or represents cyanoalkyl having1 or 2 carbon atoms in the alkyl part, or represents cycloalkyl having 3to 6 carbon atoms, or represents phenyl or phenylalkyl having 1 to 3carbon atoms in the alkyl part and in each case optionally substitutedby one to three identical or different substituents from the groupcomprising alkyl having 1 to 4 carbon atoms, fluorine, chlorine, bromineand alkoxy having 1 to 4 carbon atoms and

R represents hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having3 to 12 carbon atoms, alkinyl having 4 to 12 carbon atoms orhalogenoalkyl, halogenoalkenyl or halogenoalkinyl having in each case upto 8 carbon atoms and 1 to 10 identical or different halogen atoms, orrepresents alkoxyalkyl, alkylmercaptoalkyl or cyanoalkyl having 1 to 4carbon atoms per alkyl part, or represents phenyloxyalkyl orphenylmercaptoalkyl having 1 to 4 carbon atoms in the alkyl part, itbeing possible for the phenyl radicals to be optionally substituted byone to three identical or different substituents from the groupcomprising fluorine, chlorine, bromine and alkyl having 1 to 4 carbonatoms, or represents cycloalkyl having 3 to 8 carbon atoms andoptionally substituted by one to three identical or different alkylsubstituents having 1 to 4 carbon atoms, it being possible for thecycloalkyl ring additionally to contain a fused-on ring, or representsphenylalkyl having 1 to 4 carbon atoms in the alkyl part and optionallysubstituted by one to five identical or different substituents from thegroup comprising halogen, alkyl having 1 to 4 carbon atoms,halogenoalkyl having 1 to 4 carbon atoms and 1 to 8 identical ordifferent halogen atoms, nitro, cyano, alkoxy having 1 to 4 carbon atomsand alkylmercapto having 1 to 4 carbon atoms, the alkyl part of thephenylalkyl optionally containing, as a substituent, a further phenylradical which can optionally be substituted as described above, orrepresents phenyl which is optionally substituted by one to fiveidentical or different substituents from the group comprising halogen,nitro, alkyl having 1 to 12 carbon atoms, alkoxy, alkylmercapto,carbalkoxy, alkylsulphonylamino, alkylsulphonyl, sulphamoyl,N-alkylsulphamoyl, N,N-dialkylsulphamoyl, dialkylamino, carbamoyl,N-alkylcarbamoyl or N,N-dialkylcarbamoyl having in each case 1 to 4carbon atoms per alkyl radical, halogenoalkyl, halogenoalkoxy orhalogenoalkylmercapto having in each case 1 to 4 carbon atoms and 1 to 8identical or different halogen atoms per radical listed, phenyl,phenoxy, phenylmercapto, acyloxy having 1 to 3 carbon atoms, acyl having1 to 3 carbon atoms, phenylalkyloxy having 1 to 3 carbon atoms in thealkyl part, phenylalkylmercapto having 1 to 3 carbon atoms, acylaminohaving 1 to 3 carbon atoms, acylalkylamino having 1 to 3 carbon atomsper acyl and alkyl radical, cycloalkyl having 4 to 6 carbon atoms andcyano, or represents naphthyl, or

R and R¹, together with the nitrogen atom on which they stand, form aring having 5 to 7 ring members, which can optionally contain one or twofurther nitrogen and/or oxygen atoms and can optionally be substitutedby one to three alkyl radicals having 1 to 4 carbon atoms,

with the exception that R is not hydrogen if A represents SO or SO₂.

Particularly preferred compounds of the formula (I) are those in which

Hal represents chlorine, bromine or iodine,

A represents O, S, SO, SO₂ or NR¹, wherein

R¹ represents hydrogen, alkyl having 1 to 4 carbon atoms or alkenylhaving 3 or 4 carbon atoms, or represents phenyl, benzyl or2-phenyl-2-methylethyl which is optionally substituted by one to threealkyl substituents having 1 to 3 carbon atoms, and

R represents hydrogen, alkyl having 1 to 8 carbon atoms, alkenyl having3 to 8 carbon atoms, alkinyl having 4 to 8 carbon atoms, cyanoalkylhaving 1 to 3 carbon atoms in the alkyl part, cycloalkyl having 3 to 6carbon atoms, or represents phenyl, benzyl, phenethyl or naphthyl,optionally substituted by one to five identical or differentsubstituents from the group comprising alkyl having 1 to 12 carbonatoms, alkenyl having up to 3 carbon atoms, fluorine, chlorine, bromine,iodine, trifluoromethyl, nitro, alkoxy having 1 to 4 carbon atoms,alkylmercapto having 1 to 4 carbon atoms, dialkylamino having 1 or 2carbon atoms per alkyl radical, carbalkoxy having 1 to 2 carbon atoms,trifluoromethoxy, trifluoromethylmercapto, alkylsulphonylamino having 1or 2 carbon atoms, alkylsulphonyl having 1 or 2 carbon atoms, phenyl,phenoxy, phenylmercapto, acetoxy, acetyl, carbamoyl, sulphamoyl,N,N-dialkylsulphamoyl having 1 or 2 carbon atoms per alkyl radical,benzyloxy, benzylmercapto, formylamino, formylmethylamino, acetylamino,cyclopentyl, cyclohexyl and cyano, or

R and R¹, together with the nitrogen atom on which they stand, representpyrrolidine, piperidine, hexamethyleneimine, morpholine,N-alkylpiperazine (C₁ -C₂), pyrrole, pyrazole, imidazole or1,2,4-triazole, optionally substituted by one or two alkyl substituentshaving 1 or 2 carbon atoms,

with the exception that R is not hydrogen if A represents SO or SO₂.

Compounds of the formula (I) which are to be especially singled out arethose in which

Hal represents halogen and

A--R represents OR, wherein

R represents alkyl, alkenyl or alkinyl, or represents cycloalkyl whichis optionally substituted by one or more identical or different alkylsubstituents, it being possible for a ring to be fused on in addition tothe alkyl substitution, or represents aralkyl which is optionallysubstituted in the aryl part by one or more identical or differentsubstituents from the group comprising halogen, alkyl, halogenoalkyl,nitro, alkoxy, alkylmercapto and cyano, or represents aryl which isoptionally substituted by one or more identical or differentsubstituents from the group comprising halogen, alkyl, alkenyl,halogenoalkyl, nitro, alkoxy, alkylmercapto, dialkylamino, carbalkoxy,carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl, halogenoalkyloxy,halogenoalkylmercapto, alkylsulphonylamino, alkylsulphonyl, aryl,aryloxy, arylmercapto, acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl,N,N-dialkylsulphamoyl, aralkyloxy, aralkylmercapto, acylamino,acylalkylamino, cycloalkyl and cyano,

or

A--R represents SR, wherein represents alkyl, alkenyl or alkinyl, orrepresents cycloalkyl which is optionally substituted by one or moreidentical or different alkyl substituents, it being possible for a ringto be fused on in addition to the alkyl substitution, or representsaralkyl which is optionally substituted in the aryl part by one or moreidentical or different substituents from the group comprising halogen,alkyl, halogenoalkyl, nitro, alkoxy, alkylmercapto and cyano, orrepresents aryl which is optionally substituted by one or more identicalor different substituents from the group comprising halogen, alkyl,alkenyl, halogenoalkyl, nitro, alkoxy, alkylmercapto, dialkylamino,carbalkoxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl,halogenoalkoxy, halogenoalkylmercapto, alkylsulphonylamino,alkylsulphonyl, aryl, aryloxy, arylmercapto, acyloxy, acyl, sulphamoyl,N-alkysulphamoyl, N,N-dialkylsulphamoyl, aralkoxy, aralkylmercapto,acylamino, acylalkylamino, cycloalkyl and cyano,

or

A--R represents SO_(n) R, wherein

n represents 1 or 2 and

R represents aryl which is optionally substituted by one or moreidentical or different substituents from the group comprising halogen,alkyl, alkenyl, halogenoalkyl, nitro, alkoxy, alkylmercapto,dialkylamino, carbalkoxy, carbamoyl, N-alkylcarbamoyl,N,N-dialkylcarbamoyl, halogenoalkoxy, halogenoalkylmercapto,alkylsulphonylamino, alkylsulphonyl, aryl, aryloxy, arylmercapto,acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl,aralkyloxy, aralkylmercapto, acylamino, acylalkylamino, cycloalkyl andcyano,

or

A--R represents --NH--R, wherein

represents alkenyl, alkinyl, or represents cycloalkyl which isoptionally substituted by one or more identical or different alkylsubstituents, it being possible for a ring to be fused on in addition tothe alkyl substitution, or represents aralkyl which is optionallysubstituted in the aryl part by one or more identical or differentsubstituents from the group comprising halogen, alkyl, halogenoalkyl,nitro, alkoxy, alkylmercapto and cyano, or represents aryl which isoptionally substituted by one or more identical or differentsubstituents from the group comprising halogen, alkyl, halogenoalkyl,nitro, dialkylamino, carbalkoxy, carbamoyl, N-alkylcarbamoyl,N,N-dialkylcarbamoyl, halogenomethyloxy, halogenomethylmercapto,alkylsulphonylamino, alkylsulphonyl, aryl, aryloxy, arylmercapto,acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl,aralkyloxy, aralkylmercapto, acylamino, acylalkylamino, cycloalkyl andcyano,

or

A--R represents ##STR9## wherein R¹ represents alkyl, alkenyl,halogenoalkyl or cyanoalkyl or represents cycloalkyl, aryl or aralkyl,in each case optionally substituted by one or more identical ordifferent substituents, and

R represents alkyl, alkenyl or alkinyl, it being possible for theabovementioned radicals in each case to be optionally substituted by oneor more identical or different substituents from the group comprisinghalogen, alkoxy, aryloxy, alkylmercapto, arylmercapto and cyano, orrepresents cycloalkyl which is optionally substituted by one or moreidentical or different alkyl substituents, it being possible for a ringto be fused on in addition to the alkyl substitution, or representsaralkyl which is optionally substituted in the aryl part by one or moreidentical or different substituents from the group comprising halogen,alkyl, halogenoalkyl, nitro, alkoxy, alkylmercapto and cyano, orrepresents aryl which is optionally substituted by one or more identicalor different substituents from the group comprising halogen, alkyl,alkenyl, halogenoalkyl, nitro, dialkylamino, carbalkoxy, carbamoyl,N-alkylcarbamoyl, N,N-dialkylcarbamoyl, halogenomethyloxy,halogenomethylmercapto, alkylsulphonylamino, alkylsulphonyl, aryl,aryloxy, arylmercapto, acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl,N,N-dialkylsulphamoyl, aralkyloxy, aralkylmercapto, acylamino,acylalkylamino, cycloalkyl and cyano, or

R and R¹, together with the nitrogen atom on which they stand, form aring which can optionally be interrupted by one or more furtheridentical or different hetero atoms and can optionally be substituted byone or more identical or different substituents.

The number of carbon atoms, the substituents and the number ofsubstituents correspond to the data in the preferred definition.

If 2,4-dichloro-5-nitrothiazole and aniline are used as startingsubstances in process (a) according to the invention, the course of thereaction can be represented by the following equation: ##STR10## If2,4-dichloro-5-nitrothiazole and N,N-dimethylaniline are used asstarting substances, the course of process (b) according to theinvention can be represented by the following equation: ##STR11##

If 4-chloro-2-(4-methylphenylmercapto)-5-nitrothiazole and 2 mols of3-chloroperoxybenzoic acid are used as starting substances, the courseof process (c), variant α, according to the invention can be representedby the following equation: ##STR12##

If 4-chloro-2-(4-methylphenylmercapto)-5-nitrothiazole is used as thestarting substance and 1 mol of 3-chloroperoxybenzoic acid is used asthe oxidizing agent, the course of process (c), variant β, according tothe invention can be represented by the following equation: ##STR13##

The 2,4-dihalogeno-5-nitrothiazoles of the formula (II) required asstarting substances in process (a) according to the invention are knownin some cases, for example for compounds of the formula (II) in which

Hal=Hal¹ =bromine: Chem. Abstr. 61: 3087 f and for

Hal=Hal¹ =chlorine, compare DE-OS (German Published Specification)3,518,520.

The two compounds mentioned are producible, for example, by nitration ofthe corresponding 2,4-dihalogenothiazoles.

Compounds of the formula (II A) ##STR14## in which Hal' and Hal^(1')independently of one another represents chlorine, iodine or fluorine,with the proviso that the two Hals may not simultaneously be chlorine,

are new and likewise form part of the invention. At appropriateconcentrations, these substances also display a microbicidal action.

Thus, compounds of the formula (II A) in which

Hal'=Hal^(1') =iodine or

Hal'=chlorine and Hal^(1') =iodine or

Hal'=iodine and Hal^(1') =chlorine or

Hal'=chlorine and Hal^(1') =fluorine

for example, are new. The iodine compounds are thus obtained by reactionof 2,4-dichloro-5-nitrothiazole with metal iodides, in particular sodiumiodide, in lower aliphatic ketones, in particular acetone, as thesolvent in accordance with the following equations: ##STR15##

The two isomeric chloro-iodo-nitrothiazoles are formed side by side andcan be separated from one another by fractional crystallization and/orby chromatographic methods. The reaction temperature is in generalbetween 0° C. and 130° C., preferably between 10° C. and 90° C.

Compounds of the formula (II A) in which at least one of the halogens isfluorine, for example Hal^(1') =fluorine and Hal'=chlorine, that is tosay 4-chloro-2-fluoro-5-nitrothiazole, can be prepared by reacting2,4-dichloro-5-nitrothiazole with metal fluorides, in particular sodiumfluoride or potassium fluoride, in lower aliphatic nitriles, inparticular in acetonitrile or propionitrile, as the solvent in thepresence of catalytic amounts of crown ethers, in particular of [18]crown-6. The reaction temperature is 0° C. to 50° C., preferably 10° C.to 30° C. 2-15 mols of metal fluoride, preferably 3-12 mols of metalfluoride, are used per mol of 2,4-dichloro-5-nitrothiazole.

The nucleophiles of the formula (III) furthermore required as startingsubstances in process (a) according to the invention are known inprinciple. If specific compounds have not yet been described, they canbe prepared by known processes.

Possible solvents in carrying out process (a) according to the inventionare: aliphatic nitriles, in particular acetonitrile, open-chain orcyclic dialkylamides of aliphatic carboxylic acids, such asdimethylformamide and N,N-dimethylacetamide, and furthermoreN-methyl-2-pyrrolidinone, N-methylcaprolactam, tetramethylurea,N,N'-dimethyl-1,3-imidazolin-2-one, hexamethylphosphoric acid trisamide,dimethyl sulphoxide, dimethyl sulphone, tetramethylene sulphone(=sulpholane), tetrahydrofuran, dioxane and lower aliphatic alcohols, inparticular in connection with their associated metal salt, in particularalkali metal salt.

Cyclic ethers, such as dioxane, and above all the aprotic polarsolvents, such as dimethylformamide and N-methyl-2-pyrrolidinone, aswell as acetonitrile are preferably used.

The choice of solvents also depends on the nature of the nucleophile ofthe formula (III). If the nucleophile or its metal salt, preferablyalkali metal salt, is used in the form of an aqueous solution (such as,for example, in sodium hydroxide solution or methylamine), a mixedsystem of water and one of the solvents mentioned can also be used.

Weakly basic amines, such as, for example, pyrrole, pyrazole,diphenylamine or aniline derivatives which are substituted by negativesubstituents, such as, for example, nitro or trifluoromethyl, can bereacted particularly advantageously using aprotic polar solvents, suchas dimethylformamide or N-methyl-2-pyrrolidinone, whereas strong bases,such as, for example, aliphatic amines, such as, for example,diethylamine or morpholine, also react rapidly in dioxane oracetonitrile. The reaction temperature can be varied within wide rangesin process (a) according to the invention. The reaction is in generalcarried out between -50° C. and +150° C., preferably at -20° C. to 100°C.

Strong nucleophiles in general already react very rapidly in the desiredsense at the lower limit of the temperature range mentioned, whereasweak nucleophiles require higher temperatures and longer reaction times.

The reactions are as a rule carried out under normal pressure, but thereaction can also be carried out in closed vessels in which acorrespondingly higher pressure is then established according to thenature of the solvent and the temperature.

To bind the hydrogen halide liberated in accordance with the equation inprocess (a) according to the invention an acid-binding agent is ingeneral necessary. For this there can be used, for example: alkali metalhydroxides, carbonates or bicarbonates.

Instead of using the acid-binding agent, metal salts, preferably alkalimetal salts, of the nucleophile of the formula (III) in question canalso be reacted directly. The salts can either be used as such orproduced in situ, for example by addition of alkali metal hydrides,preferably sodium hydride.

If the nucleophiles to be employed are strongly basic amines, such as,for example, diethylamine, a corresponding excess of the nucleophile canserve as the acidbinding agent. More weakly basic amines, such asanilines, which are reacted in aprotic, strongly polar solvents, such asdimethylformamide or N-methyl-2-pyrrolidinone, give the desiredcompounds of the formula (I) in good yields without the addition of anacid-binding agent and without using an excess of the nucleophile.

Very weak nucleophiles of the formula (III), for example anilinessubstituted by two or more negative substituents, especially those whichhave these negative substituents in the ortho-positions relative to theamino group, are advantageously reacted in ethers, in particular incyclic ethers, such as, for example, tetrahydrofuran or dioxane, withthe addition of metal hydrides, preferably sodium hydride, for thepurpose of salt formation in situ.

The reaction partners are in general reacted with one another in thestoichiometrically equimolar ratio, and in the case of strongly basicamines, which can simultaneously function as the acid-binding agent, intwice the molar ratio.

Since the 2,4-dihalogeno-5-nitrothiazoles of the formula (II) carry asecond--although of a reactivity which is a significant steplower--halogen atom in the 4-position, it is generally advantageous notto employ an excess of nucleophile of the formula (III). In certaincases, however, it may be advantageous to employ an excess of2,4-dihalogeno-5-nitrothiazole of the formula (II), which can in generalbe 20 mol percent up to 100 mol percent. In the case of weaknucleophiles of the formula (III) which react only relatively slowlywith the considerably more reactive halogen in the 2-position of thethiazole ring, on the other hand, an excess of the nucleophile of theformula (III), which can be up to 100 mol percent, can be employed.

In carrying out process (a) according to the invention, the2,4-dihalogeno-5-nitrothiazole of the formula (II) is preferablyinitially introduced into one of the solvents mentioned and theacid-binding agent is then added, if appropriate. The nucleophile of theformula (III) is then slowly added in small portions, for example bydropwise addition of a solution or in a diluent, at room temperature orbelow, particularly preferably down to -15° C. Local excesses ofnucleophile of the formula (III) during reaction with the2,4-dihalogeno-5-nitrothiazole of the formula (II) are to the greatestextent avoided by this measure of slow addition, and formation ofdisubstitution products which are undersirable here is thus virtuallyexcluded.

If the desired final reaction temperature is to be above roomtemperature, the mixture is subsequently heated.

The reaction products are isolated by customary methods. In the simplestcase, the reaction mixture is stirred into excess ice-water, for example5 to 10 times the amount by volume of the solvent employed, ifappropriate after partial or complete removal of the solvent bydistillation in vacuo below the reaction temperature, and the product isfiltered off, washed with water and dried. If an excess of2,4-dihalogeno-5-nitrothiazole has been used, this can be dissolved outof the well-dried crude product by stirring at room temperature with asolvent which dissolves virtually only the2,4-dihalogeno-5-nitrothiazole of the formula (II), and if appropriatecan be re-used for subsequent batches. In the case of2,4-dichloro-5-nitrothiazole, petroleum ether, for example, isparticularly suitable. If the reaction product which still containsexcess 2,4-dihalogeno-5-nitrothiazole of the formula (II) is itselfreadily soluble in petroleum ether at room temperature, the2,4-dihalogeno-5-nitrothiazole of the formula (II) is subjected, forexample, to fractional sublimation or distillation from the usuallysignificantly less volatile reaction product in vacuo under about 0.1mbar. In the case of 2,4-dichloro-5-nitrothiazole this is possible, forexample, at a temperature of about 70° C. under 0.1 mbar. Furtherpurification of the reaction products can be effected, for example, byrecrystallization or by a chromatographic route.

If a reaction product is obtained as an oil when the mixture is stirredin excess ice-water, it is isolated by extraction several times byshaking with one of the usual organic water-immiscible solvents, suchas, for example, methylene chloride, by separating off the organicphase, washing it with water if appropriate, for example in the case ofdimethylformamide or N-methyl-2-pyrrolidinone as the reaction medium,drying it and concentrating it in vacuo.

The N,N-dimethylarylamines of the formula (IV) required as startingsubstances in process (b) according to the invention are known inprinciple. If specific compounds have not yet been described, they canbe prepared by known methods. In formula (IV), aryl has the same meaningas aryl in the definition of R in formula (I).

Possible solvents in carrying out process (b) according to the inventionare aliphatic or aromatic nitriles, for example acetonitrile,propionitrile or benzonitrile, in particular acetonitrile, and ethers,in particular cyclic ethers, such as dioxane and tetrahydrofuran, inparticular dioxane.

The reaction temperature can be varied within wide ranges in process (b)according to the invention. The reaction is in general carried outbetween 50° C. and 200° C., preferably at 60° C. to 150° C.

The reactions are as a rule carried out under normal pressure, but thereaction can also be carried out in closed vessels in which acorrespondingly higher pressure is then established according to thenature of the solvent and the temperature.

The reaction partners are preferably reacted with one another instoichiometrically equimolar ratio.

In carrying out process (b) according to the invention, the2,4-dihalogeno-5-nitrothiazole of the formula (II) is preferablydissolved in one of the solvents mentioned, preferably the approximatelyequimolar amount of N,N-dimethylarylamine is added and the mixture isheated, preferably under reflux, until the reaction has virtually ended.The solvent is then distilled off, preferably in vacuo, and the residueis purified, if necessary, for example by recrystallization.

Formula (V) provides a definition of the 4-halogeno-5-nitrothiazolylsulphides according to the invention required as starting substances inprocess (c) according to the invention. In this formula, Hal and Rpreferably represent those radicals which have already been mentioned inconnection with the description of the substances of the formula (I)according to the invention.

All the customary reagents which can be used for such purposes can beemployed as oxidizing agents in process (c) according to the invention.Aliphatic or aromatic percarboxylic acids, such as, for example,peracetic acid, perpropionic acid and 3-chloroperbenzoic acid, arepreferred. 3-Chloroperbenzoic acid is particularly preferred.

All the customary inert organic solvents can be used as solvents inprocess (c) according to the invention. Preferred possible solvents aremethylene chloride, chloroform and carbon tetrachloride.

The reaction temperatures can be varied within a certain range inprocess (c) according to the invention. The reaction is in generalcarried out at temperatures between 0° C. and 100° C., preferablybetween 20° C. and 80° C.

In carrying out process (c), variant α, according to the invention, the4-halogeno-5-nitrothiazolyl sulphide of the formula (V) is in generaldissolved in one of the solvents mentioned and at least 2 mols of anoxidizing agent, preferably one of the percarboxylic acids mentioned,preferably up to 5 mols of oxidizing agent per mol of the compound ofthe formula (V), are added and the mixture is stirred, for example whilemonitoring by thin layer chromatography, until the desired reaction hasended. Reflux conditions are preferably used here in order to acceleratethe reaction.

In carrying out process (c), variant β, according to the invention, the4-halogeno-5-nitrothiazolyl sulphide of the formula (V) is dissolved inone of the solvents mentioned and small portions of oxidizing agent,preferably percarboxylic acid, are added to avoid sulphone formationwhich is undesirable here, preferably in the lower range of the reactiontemperature mentioned, for example at room temperature, the reactionbeing monitored by thin layer chromatography. The total amount ofoxidizing agent, for example percarboxylic acid, is preferably in therange from 1 to 1.5 mols per mol of compound of the formula (V). Sincethe reaction of course proceeds relatively slowly at low temperatures,for example at room temperature, the reaction can be stopped with theaid of thin layer chromatography, even when more than 1 mol ofpercarboxylic acid is used per mol of compound of the formula (V),before noticeable amounts of undesirable sulphone are formed.

The sulphones or sulphoxides are isolated in the pure form in thecustomary manner. The solvent is stripped off in vacuo, the residue isstirred with excess aqueous sodium bicarbonate solution at roomtemperature, in order to remove, for example, the (per)carboxylic acids,the mixture is filtered and the residue is washed with water, dried andif appropriate recrystallized, for example from hydrocarbons, such ascyclohexane.

The active compounds of the formula (I) according to the invention havea potent action against pests and can be used in practice for combatingundesirable harmful organisms. The active compounds are suitable for useas plant protection agents, above all as fungicides and in addition forprotecting industrial materials against microbes, such as, for example,fungi, bacteria and slime organisms.

Fungicidal agents in plant protection are employed for combatingPlasmodiophoromycetes, Oomycetes, Chytridiomycetes, Zygomycetes,Ascomycetes, Basidiomycetes and Deuteromycetes. Bactericidal agents areemployed in plant protection for combating Pseudomonadaceae,Rhizobiaceae, Enterobacteriaceae, Corynebacteriaceae andStreptomycetaceae.

Some causative organisms of fungal and bacterial diseases which comeunder the generic names listed above may be mentioned as examples, butnot by way of limitation: Xanthomonas species, such as, for example,Xanthomonas campestris pv. oryzae; Pseudomonas species, such as, forexample, Pseudomonas syringae pv. lachrymans; Erwinia species, such as,for example, Erwinia amylovora; Pythium species, such as, for example,Pythium ultimum; Phytophthora species, such as, for example,Phytophthora infestans; Pseudoperonospora species, such as, for example,Pseudoperonospora humuli or Pseudoperonospora cubensis; Plasmoparaspecies, such as, for example, Plasmopara viticola; Peronospora species,such as, for example, Peronospora pisi or P. brassicae; Erysiphespecies, such as, for example, Erysiphe graminis; Sphaerotheca species,such as, for example, Sphaerotheca fuliginea; Podosphaera species, suchas, for example, Podosphaera leucotricha; Venturia species, such as, forexample, Venturia inaequalis; Pyrenophora species, such as, for example,Pyrenophora teres or P. graminea (conidia form: Drechslera, syn:Helminthosporium); Cochliobolus species, such as, for example,Cochliobolus sativus (conidia form: Drechslera, syn: Helminthosporium);Uromyces species, such as, for example, Uromyces appendiculatus;Puccinia species, such as, for example, Puccinia recondita; Tilletiaspecies, such as, for example, Tilletia caries; Utilago species, suchas, for example, Ustilago nuda or Ustilago avenae; Pellicularia species,such as, for example, Pellicularia sasakii; Pyricularia species, suchas, for example, Pyricularia oryzae; Fusarium species, such as, forexample, Fusarium culmorum; Botrytis species, such as, for example,Botrytis cinerea; Septoria species, such as, for example, Septorianodorum; Leptosphaeria species, such as, for example, Leptosphaerianodorum; Cercospora species, such as, for example, Cercospora canescens;Alternaria species, such as, for example, Alternaria brassicae andPseudocercosporella species, such as, for example, Pseudocercosporellaherpotrichoides.

The good toleration, by plants, of the active compounds, at theconcentrations required for combating plant diseases, permits treatmentof above-ground parts of plants, of vegetative propagation stock andseeds, and of the soil.

The active compounds according to the invention can be used withparticularly good success here for combating fruit, vegetable and cerealdiseases, such as, for example, against the apple scab causativeorganism (Venturia inaequalis), the brown rot of tomato causativeorganism (Phytophthora infestans), vine disease causative organisms(Plasmopara viticola) or cereal disease causative organisms, such as,for example, Leptosphaeria nodorum, Fasarium nivale and Pyrenophorateres. The action against the rice spot disease causative organisms(Pyricularia oryzae) and the broad in vitro action may also bementioned. When used in appropriate concentrations, many of thecompounds according to the invention also have a bactericidal action.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, very fine capsules in polymeric substances and incoating compositions for seed, as well as ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurfaceactive agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethyl sulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example groundnatural minerals; such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly-dispersed silicic acid, alumina and silicates.As solid carriers for granules there are suitable: for example crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks. As emulsifying and/or foam-formingagents there are suitable: for example non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers, alkyl sulphonates, alkyl sulphates, aryl sulphonates as well asalbumin hydrolysis products. As dispersing agents there are suitable:for example ligninsulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, as well as naturalphospholipids, such as cephalins and lecithins, and syntheticphospholipids, can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, as well as inmixtures with fertilizers and growth regulators.

The active compounds can be used as such or in the form of theirformulations or the use forms prepared therefrom, such as ready-to-usesolutions, emulsifiable concentrates, emulsions, foams, suspensions,wettable powders, pastes, soluble powders, dusts and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, dusting, foaming, brushing on and the like. It isfurthermore possible to apply the active compounds by the ultra-lowvolume method or to inject the active compound formulation or the activecompound itself into the soil. The seeds of the plants can also betreated.

In the treatment of parts of plants, the active compound concentrationsin the use forms can be varied within a substantial range. They are, ingeneral, between 1 and 0.0001% by weight, preferably between 0.5 and0.001%.

In the treatment of seed, amounts of active compound of 0.001 to 50 gper kilogram of seed, preferably 0.01 to 10 g, are generally required.

For the treatment of soil, active compound concentrations of 0.00001 to0.1% by weight, preferably 0.0001 to 0.02%, are required at the place ofaction.

Due to their broad range of action, the active compounds of the formula(I) according to the invention are furthermore suitable for theprotection of industrial materials.

Since industrial materials can be infested and damaged by very many anda wide variety of microbe species, a broad range of action which alsomakes possible a wide range of uses is an essential property of advancedmaterial protection compounds.

According to the invention, industrial materials are nonliving materialswhich have been prepared for use in industry. For example, industrialmaterials which are to be protected by active compounds according to theinvention against change or destruction by microbes are adhesives,glues, paper and board, textiles, leather, wood, paints and plasticarticles, cooling lubricants and other materials which can be infestedor destroyed by microorganisms. Within the context of materials to beprotected, parts of production plants, for example coolingwatercircuits, which can be impaired by multiplication of microorganisms, mayalso be mentioned. In the context of the present invention, industrialmaterials which may be mentioned are preferably adhesives, glues, papersand boards, leather, wood, paints, cooling lubricants and coolingcircuits.

Examples of microorganisms which can cause degradation or change inindustrial materials are bacteria, fungi, yeasts, algae and slimeorganisms. The active compounds according to the invention preferablyact against fungi, in particular mold fungi, fungi which discolor anddestroy wood (Basidiomycetes), and against slime organisms and algae.

Examples of microorganisms which may be mentioned are those of thefollowing genera:

Alternaria, such as Alternaria tenuis,

Aspergillus, such as Aspergillus niger,

Chaetomium, such as Chaetomium globosum,

Coniophora, such as Coniophora puteana,

Lentinus, such as Lentinus tigrinus,

Penicillium, such as Penicillium glaucum,

Polyporus, such as Polyporus versicolor,

Aureobasidium, such as Aureobasidium pullulans,

Sclerophoma, such as Sclerophoma pityophila,

Trichoderma, such as Trichoderma viride,

Escherichia, such as Escherichia coli,

Pseudomonas, such as Pseudomonas aeruginosa,

Staphylococcus, such as Staphylococcus aureus.

Depending on the area of application, an active compound according tothe invention can be converted into the customary formulations, such assolutions, emulsions, suspensions, powders, pastes and granules.

These can be prepared in a known manner, for example by mixing theactive compounds with an extender which comprises liquid solvent and/orsolid carriers, if appropriate using surface-active agents, such asemulsifiers and/or dispersants, it being possible, if appropriate, touse organic solvents such as alcohols as auxiliaries in the case of theuse of water as extender.

Liquid solvents for the active compounds can be, for example, water,alcohols, such as lower aliphatic alcohols, preferably ethanol orisopropanol, or benzyl alcohol, ketones, such as acetone or methyl ethylketone, liquid hydrocarbons, such as petroleum fractions, andhalogenated hydrocarbons, such as 1,2-dichloroethane.

Microbicidal agents generally contain the active compounds in an amountof from 1 to 95%, preferably 10 to 75%.

The use concentrations of the active compounds according to theinvention depend on the species and occurrence of the microorganisms tobe controlled, and on the composition of the material to be protected.The optimum amounts used can be determined by series of tests. Ingeneral, the use concentrations are in the range from 0.001 to 5% byweight, preferably 0.05 to 1.0% by weight, relative to the material tobe protected.

The active compounds according to the invention can also be in the formof a mixture with other known active compounds. The following activecompounds may be mentioned as examples: benzyl alcoholmono(poly)hemiformal and other formaldehyde-eliminating compounds,benzimidazolyl methylcarbamates, tetramethylthiuram disulphide, zincsalts of dialkyl dithiocarbamates, 2,5,5,6-tetrachloroisophthalonitrile,thiazolylbenzimidazole, mercaptobenzothiazole,2-thiocyanatomethylthiobenzothiazole, methylene bisthiocyanate, phenolderivatives, such as 2-phenylphenol,(2,2'-dihydroxy-5,5'-dichloro)-diphenylmethane and3-methyl-4-chloro-phenol, and organotin compounds.

PREPARATION EXAMPLES EXAMPLE 1 ##STR16##

A solution of 8.6 g (0.05 mol) of 3-bromoaniline in 100 ml ofdimethylformamide is added dropwise to a solution of 12.0 g (0.06 mol)of 2,4-dichloro-5-nitrothiazole in 100 ml of dimethylformamide at 0° C.to 5° C. in the course of about 2 hours and the mixture is subsequentlystirred at the same temperature for a further 4 hours. It is thenstirred into 1,000 ml of ice-water and the precipitate is filtered off,washed with water and dried. To remove excess2,4-dichloro-5-nitrothiazole, the product is stirred in 80 ml ofpetroleum ether at room temperature, filtered off, washed with petroleumether and dried. 16.0 g (95.7% of theory) of2-(3bromophenylamino)-4-chloro-5-nitrothiazole of melting point 191° C.to 192° C. (decomposition) are thus obtained.

EXAMPLE 2 ##STR17##

42 g (0.036 mol) of anhydrous potassium carbonate are added to asolution of 72.0 g (0.36 mol) of 2,4-dichloro-5-nitrothiazole in 300 mlof acetonitrile. A solution of 28.2 g (0.3 mol) of phenol in 300 ml ofacetonitrile is then added dropwise at 15° C. to 20° C. in the course ofabout 1.5 hours and the mixture is subsequently stirred at the sametemperature for a further 0.5 hour. It is then heated at the refluxtemperature for 15 minutes, cooled to room temperature and then stirredinto 3 liters of ice-water and the precipitate is filtered off, washedwith water and dried. To remove excess 2,4-dichloro-5-nitrothiazole, theproduct is stirred in 500 ml of petroleum ether at about 20° C.,filtered off, washed with petroleum ether and dried. 75.4 g (98.0% oftheory) of 4-chloro-5-nitro-2-phenoxythiazole are thus obtained. Meltingpoint 96° C. (from petroleum ether).

EXAMPLE 3 ##STR18##

146 g (2 mols) of diethylamine are added dropwise to a solution of 199 g(1 mol) of 2,4-dichloro-5-nitrothiazole in 1 l of dioxane at 20° C. to30° C. in the course of about 2 hours. After the mixture has been leftto stand overnight at room temperature, it is stirred in 8 l of icewaterand the precipitate is filtered off, washed with water and dried. 216 g(91.7% of theory) of 2-diethylamino-4-chloro-5-nitrothiazole of meltingpoint 85° C. (from cyclohexane) are obtained.

EXAMPLE 4 ##STR19##

252 g (3.0 mols) of sodium bicarbonate are added to a solution of 360 g(1.8 mols) of 2,4-dichloro-5-nitrothiazole in 1.5 l of acetonitrile. Amixture of 139.5 g (1.5 mols) of aniline and 1,500 ml of acetonitrile isthen added dropwise at -10° C. to -15° C. in the course of about 4.5hours and the mixture is subsequently stirred at the same temperaturefor a further 4 hours. It is then stirred into 15 l of ice-water and theprecipitate is filtered off, washed with water and dried. To removeexcess 2,4-dichloro-5-nitrothiazole, the product is stirred into 2.4 lof petroleum ether at room temperature, filtered off, washed withpetroleum ether and dried. 361.7 g (94.4% of theory) of2-anilino-4-chloro-5-nitrothiazole of melting point 186° C. to 187° C.(decomposition) are obtained.

EXAMPLE 5 ##STR20##

10.1 g (0.105 mol) of ammonium carbonate are added to a solution of 19.9g (0.1 mol) of 2,4-dichloro-5-nitrothiazole in 200 ml of acetonitrile,while stirring, and stirring is continued at room temperature for twodays. The mixture is then stirred into 1 l of ice-water and theprecipitate is filtered off, washed with water and dried. To removeunreacted 2,4-dichloro-5-nitrothiazole, the product is stirred intoabout 100 ml of petroleum ether at room temperature, filtered off,washed with petroleum ether and dried. 12.2 g (68.0% of theory) of2-amino-4-chloro-5-nitrothiazole of melting point 180° C.(decomposition) are obtained.

EXAMPLE 6 ##STR21##

4.1 g (0.05 mol) of 3-methylpyrazole are added to a solution of 5.0 g(0.025 mol) of 2,4-dichloro-5-nitrothiazole in 50 ml ofN-methyl-2-pyrrolidinone at room temperature. After the mixture has beenleft to stand at room temperature for four days, it is stirred into 500ml of ice-water and the precipitate is filtered off, washed with waterand dried. 5.8 g (94.9% of theory) of4-chloro-2-(3-methyl-1-pyrazolyl)-5-nitrothiazole of melting point 153°C. are obtained.

EXAMPLE 7 ##STR22##

200 ml (0.2 mol) of an aqueous 1N sodium hydroxide solution are slowlyadded dropwise to a solution of 19.9 g (0.1 mol) of2,4-dichloro-5-nitrothiazole in 200 ml of dioxane at 20° C. to 25° C.After stirring has been continued overnight at room temperature, themixture is acidified with concentrated hydrochloric acid at 0° C. to 5°C. A total of 13.3 g (73.7% of theory) of4-chloro-2-hydroxy-5-nitrothiazole and the desmotropic keto formformulated above, of melting point 136° C. (decomposition) are obtainedby concentrating the resulting suspension to about one quarter of itsvolume at room temperature in vacuo.

EXAMPLE 8 ##STR23##

7.0 g (0.051 mol) of anhydrous potassium carbonate are added to asolution of 12.0 g (0.06 mol) of 2,4-dichloro-5-nitrothiazole in 50 mlof acetonitrile. A mixture of 5.35 g (0.05 mol) of benzylamine and 50 mlof acetonitrile is then added dropwise at 15° C. to 20° C. in the courseof about half an hour and the mixture is subsequently stirred at roomtemperature for a further hour. It is then heated at the refluxtemperature for 15 minutes, cooled to room temperature and stirred intoabout 500 ml of ice-water and the precipitate is filtered off, washedwith water and dried. To remove excess 2,4-dichloro-5-nitrothiazole, theproduct is stirred into 80 ml of petroleum ether at room temperature,filtered off, washed with petroleum ether and dried. 12.9 g (95.7% oftheory) of 2-benzylamino-4-chloro-5-nitrothiazole of melting point 195°C. to 196° C. (decomposition) are obtained.

EXAMPLE 9 ##STR24##

A mixture of 28.8 g (0.16 mol) of 30% strength sodium methanolatesolution in methanol and 40 ml of methanol is added dropwise to asolution of 19.9 g (0.1 mol) of 2,4-dichloro-5-nitrothiazole in 100 mlof methanol at 0° C. to 5° C. in the course of about 1.5 hours and themixture is subsequently stirred at room temperature for about a furtherhour. After the solvent has been stripped off at room temperature invacuo, the residue is stirred with a mixture of 180 ml of 1Nhydrochloric acid and 90 ml of water and the precipitate is filteredoff, washed with water and dried. Yield: 9.9 g (50.9% of theory) of4-chloro-2-methoxy-5-nitrothiazole of melting point 52° C. (frompetroleum ether).

EXAMPLE 10 ##STR25##

6.7 g (0.1 mol) of pyrrole are added to a solution of 10.0 g (0.05 mol)of 2,4-dichloro-5-nitrothiazole in 100 ml of N-methyl-2-pyrrolidinone atroom temperature. The mixture is then heated at 70° C. for 5 hours andsubsequently cooled to room temperature and stirred into 1 l ofice-water. The precipitate formed is filtered off, washed with water anddried. 8.25 g (72.0% of theory) of4-chloro-5-nitro-2-(1-pyrrolyl)-thiazole of melting point 138° C. to139° C. (yellow needles from toluene) are obtained.

EXAMPLE 11 ##STR26##

48.6 g (0.5 mol) of 31.9% strength aqueous methylamine solution areslowly added dropwise to a solution of 99.5 g (0.5 mol) of2,4-dichloro-5-nitrothiazole in 1,000 ml of acetonitrile at -10° C., to0° C., whereupon a precipitate separates out. After the mixture has beenfurther stirred overnight at room temperature, it is stirred into 5 l ofice-water and the precipitate is filtered off, washed with water anddried. After stirring with about 500 ml of petroleum ether at roomtemperature, the product is filtered off, washed with petroleum etherand dried. 46.9 g (48.5% of theory, based on2,4-dichloro-5-nitrothiazole, or 97% of theory, based on methylamine) of4-chloro-2-methylamino-5-nitrothiazole of melting point 212° C.(decomposition) are obtained. The compound can be recrystallized frommethanol and can be sublimed at 140° C./0.1 mbar.

EXAMPLE 12 ##STR27##

A solution, prepared by heating, of 8.9 g (0.05 mol) of ##STR28## in 50ml of dimethylformamide is slowly added dropwise to a solution of 19.9 g(0.1 mol) of 2,4-dichloro-5-nitrothiazole in 500 ml of dimethylformamideat 0° C. to 5° C., whereupon a precipitate separates out. After themixture has been subsequently stirred at 0° C. to 5° C. for six hours,it is stirred into 5 l of ice-water and the precipitate is filtered off,washed with water and dried. 9.5 g (59.7% of theory) of4-chloro-2-(4-methylphenylsulphonyl)-5-nitrothiazole are obtained. Thecompound can be recrystallized from cyclohexane and can be sublimed at140° C./0.1 mbar. Melting point 153° C. to 153.5° C.

EXAMPLE 13 ##STR29##

15.65 g (0.09 mol) of 3-chloroperxybenzoic acid are added to a solutionof 5.73 g (0.02 mol) of4-chloro-2-(4-methylphenylmercapto)-5-nitrothiazole (compound No. 57according to the invention) in 200 ml of methylene chloride and themixture is stirred under reflux for 8 hours. After cooling, the3-chlorobenzoic acid which has precipitated is first filtered off. Thefiltrate is concentrated to dryness at a room temperature in vacuo andthe residue which remains is stirred intensively with excess aqueoussodium bicarbonate solution, filtered off, washed with water and dried.6.2 g (97.3% of theory) of4-chloro-2-(4-methylphenylsulphonyl)-5-nitrothiazole, which is identicalin all its properties to the compound obtained in Example 12 areobtained.

EXAMPLE 14 ##STR30##

A total of 4.35 g (0.025 mol) of 3-chloroperoxybenzoic acid are added inportions (about 8 portions) to a solution of 5.2 g (0.018 mol) of4-chloro-2-(4-methylphenylmercapto)-5-nitrothiazole (compound No. 57according to the invention) in 200 ml of methylene chloride at roomtemperature in the course of about 50 hours. The mixture is thenconcentrated to dryness in vacuo at room temperature and the residuewhich remains is stirred intensively with excess aqueous sodiumbicarbonate solution, filtered off, washed with water and dried.4-Chloro-2-(4-methylphenylsulphinyl)-5-nitrothiazole of melting point112° C. (from cyclohexane) is obtained.

EXAMPLE 15 ##STR31##

Compound No. 107 is prepared analogously to Example 2 from2,4-dichloro-5-nitrothiazole and t-butylmercaptan. The oil formed afterstirring the mixture into excess icewater is taken up in methylenechloride and the methylene chloride phase is separated off, dried withanhydrous sodium sulphate and concentrated in vacuo. Excess2,4-dichloro-5-nitrothiazole is removed by high vacuum distillation in aflash distillation apparatus up to a heating bath temperature of 70° C.under 0.1 mbar and pure 2-tert.-butylmercapto-4-chloro-5-nitrothiazoleis then distilled at a heating bath temperature of about 80° C./0.1mbar.

EXAMPLE 16 ##STR32##

12.7 g (0.105 mol) of N,N-dimethylaniline are added to a solution of19.9 g (0.1 mol) of 2,4-dichloro-5-nitrothiazole in 250 ml ofacetonitrile and the reaction mixture is stirred under reflux for 75hours. The solvent is then stripped off in vacuo and the solid residueis stirred into water, filtered off, washed with water and dried. 25.8 g(95.7 % of theory) of4-chloro-2-(N-methyl-N-phenylamino)-5-nitrothiazole are obtained. Thecompound can be recrystallized from cyclohexane and can be sublimed atabout 110° C. to 120° C./0.1 mbar. Melting point 136° C. to 137° C.

It is also possible to prepare compound No. 13 analogously to Example 2.

PREPARATION OF STARTING SUBSTANCES WHICH ARE NOT YET KNOWN FROM THELITERATURE EXAMPLE A1 ##STR33##

19.9 g (0.1 mol) of 2,4-dichloro-5-nitrothiazole are dissolved in 500 mlof acetone and, after addition of 150 g (1 mol) of sodium iodide, themixture is stirred under reflux for about 60 hours. Thereafter, thecontent of 2,4-diiodo-5-nitrothiazole in the reaction mixture is morethan 95%, according to analysis by gas chromatography. The solvent isthen stripped off in vacuo and the residue is stirred into water,filtered off, washed with water and dried. 33.9 g (89% of theory) of2,4-diiodo-5-nitrothiazole of melting point 135° C. are obtained afterrecrystallization from cyclohexane.

EXAMPLE A2 ##STR34##

39.8 g (0.2 mol) of 2,4-dichloro-5-nitrothiazole are dissolved in 500 mlof acetone and, after addition of 90 g (0.6 mol) of sodium iodide, themixture is stirred at room temperature for about 6 days, the progress ofthe reaction being monitored by gas chromatography. The solvent is thenstripped off in vacuo and the residue is stirred into water, filteredoff, washed with water and dried. A substance mixture which, accordingto analysis by gas chromatography, contains 71.5% of2-iodo-4-chloro-5-nitrothiazole and 25.8% of2-chloro-4-iodo-5-nitrothiazole is obtained. HPLC (=high pressure liquidchromatography) chromatographic separation gave the pure substances withthe following melting points:

2-iodo-4-chloro-5-nitrothiazole: melting point 80° C.-81° C.,

2-chloro-4-iodo-5-nitrothiazole: melting point 108° C.-109.5° C.

EXAMPLE A3 ##STR35##

19.9 g (0.1 mol) of 2,4-dichloro-5-nitrothiazole are dissolved in 60 mlof acetonitrile and, after addition of 24 g (0.4 mol) of calcinedpotassium fluoride and 0.5 g of [18] crown-6, the mixture is stirred atroom temperature for about one week, the progress of the reaction beingmonitored by gas chromatography. The crude batch is distilled under 0.1to 0.2 mbar at a temperature of 20 ° to 25° C., the volatileconstituents being collected in a receiver cooled with methanol/dry ice.The acetonitrile is then distilled off under normal pressure, a mixtureof approximately equal parts of 4-chloro-2-fluoro-5-nitrothiazole and2,4-dichloro-5-nitrothiazole remaining. The4-chloro-2-fluoro-5-nitrothiazole can be separated off from thismixture, for example, by fractional distillation.

¹⁹ F-NMR (CDCl₃) (CF₃ -COOH as the external standard): =-17.5 ppm.

    ______________________________________                                        MS:         182 (37%) = M.sup.+ = C.sub.3 ClFN.sub.2 O.sub.2 S                            124 (34%)                                                                      91 (60%)                                                                      63 (100%)                                                        ______________________________________                                    

The isomeric 2-chloro-4-fluoro-5-nitrothiazole can be identified by gaschromatography as a secondary component in a relative amount of between1 and 5%, based on the 4-chloro-2-fluoro-5-nitrothiazole.

¹⁹ F-NMR (CDCL₃) (CF₃ -COOH as the external standard): =-22.7 ppm.

    ______________________________________                                        MS:         182 (83%) = M.sup.+ = C.sub.3 ClFN.sub.2 O.sub.2 S                            136 (32%)                                                                      91 (43%)                                                                      75 (100%)                                                        ______________________________________                                    

The following 4-halogeno-5-nitrothiazole derivatives of the generalformula (I) are obtained in a corresponding manner and in accordancewith the general instructions on the preparation.

    __________________________________________________________________________     ##STR36##                                              (I)                   Compound                          Melting Point (°C.)                  Number                                                                              Hal                                                                              A       R                (recrystallized from)                                                                    Preparation                      __________________________________________________________________________    1     Cl                                                                                ##STR37##                                                                            C.sub.2 H.sub.5   85 (Cyclohexane)                                                                        see Example 3                    2     Cl                                                                                ##STR38##               135 (Ethanol)                                                                            analogously to Example 3         3     Cl NH      H                180        see Example 5                                                      decomposition                               4     Cl                                                                                ##STR39##               122 (Cyclohexane)                                                                        analogously to Example 6         5     Cl NH                                                                                     ##STR40##       190-1 decomposition                                                                      analogously to Example 1 and                                                  see Example 4                    6     Cl                                                                                ##STR41##               147 (Cyclohexane)                                                                        analogously to Example 6         7     Cl                                                                                ##STR42##               150 decomposition                                                                        analogously to Example 6         8     Cl NH                                                                                     ##STR43##       207 decomposition                                                                        analogously to Example 4         9     Cl O                                                                                      ##STR44##        94 (Methanol)                                                                           analogously to Example 2         10    Cl NH                                                                                     ##STR45##       121        analogously to Example 1         11    Cl                                                                                ##STR46##               153        see Example 6                    12    Cl                                                                                ##STR47##               205        analogously to Example 6         13    Cl                                                                                ##STR48##                                                                             ##STR49##       136-7 Cyclohexane                                                                        analogously to Example 2 and                                                  see Example 16                   14    Cl                                                                                ##STR50##                                                                             ##STR51##        93-4 Cyclohexane                                                                        analogously to Example 2         15    Cl                                                                                ##STR52##                                                                             ##STR53##        81        analogously to Example 2         16    Cl                                                                                ##STR54##                                                                             ##STR55##       118-20     analogously to Example 1         17    Cl O       H                136        see Example 7 present as                                                       ##STR56##                       18    Cl NH                                                                                     ##STR57##       195-6 decomposition                                                                      see Example 8                    19    Cl NH                                                                                     ##STR58##       130-1 (Cyclohexane)                                                                      analogously to Example 2         20    Cl                                                                                ##STR59##                                                                             ##STR60##       112-3 (Cyclohexane)                                                                      analogously to Example 2         21    Cl NH      C(CH.sub.3).sub.3                                                                              175-6      analogously to Example 2                                           (Acetonitrile)                              22    Cl NH                                                                                     ##STR61##       151 decomposition                                                                        analogously to Example 1         23    Cl NH                                                                                     ##STR62##       197 decomposition                                                                        analogously to Example 1         24    Cl NH                                                                                     ##STR63##       108-11     analogously to Example 1         25    Cl NH                                                                                     ##STR64##       188-9 decomposition                                                                      analogously to Example 1         26    Cl NH                                                                                     ##STR65##       136-8 decomposition                                                                      analogously to Example 1         27    Cl NH                                                                                     ##STR66##       214-5 decomposition                                                                      analogously to Example 1         28    Cl NH                                                                                     ##STR67##       142-4 decomposition                                                                      analogously to Example 1         29    Cl                                                                                ##STR68##                                                                             ##STR69##       decomposition 171-3                                                                      analogously to Example 10        30    Cl NH                                                                                     ##STR70##       194 decomposition                                                                        analogously to Example 1         31    Cl NH                                                                                     ##STR71##       175        analogously to Example 1         32    Cl NH                                                                                     ##STR72##       177-8 decomposition                                                                      analogously to Example 1         33    Cl NH                                                                                     ##STR73##       179-80 decomposition                                                                     analogously to Example 1         34    Cl NH                                                                                     ##STR74##       215-6 decomposition                                                                      analogously to Example 1         35    Cl NH                                                                                     ##STR75##       183-5 decomposition                                                                      analogously to Example 1         36    Cl NH                                                                                     ##STR76##       202 decomposition                                                                        analogously to Example 1         37    Cl                                                                                ##STR77##                                                                             ##STR78##       123-4      analogously to Example 1         38    Cl NH                                                                                     ##STR79##       216-7 decomposition                                                                      analogously to Example 1         39    Cl NH                                                                                     ##STR80##       170 decomposition                                                                        analogously to Example 1         40    Cl NH                                                                                     ##STR81##       243-4 decomposition                                                                      analogously to Example 1         41    Cl NH                                                                                     ##STR82##       193 decomposition                                                                        analogously to Example 4         42    I  NH                                                                                     ##STR83##       168-9 decomposition (Cyclohexane)                                                        analogously to Example 1                                                      (from 2,4-Diiodo-5- nitrothia                                                 zole)                            43    Cl NH                                                                                     ##STR84##       185-6 decomposition                                                                      analogously to Example 1         44    Cl NH                                                                                     ##STR85##       175- 6 decomposition                                                                     analogously to Example 1         45    Cl O       CH.sub.3          52        see Example 9                                                      (petroleum ether)                           46    Cl NH                                                                                     ##STR86##       178-9 decomposition                                                                      analogously to Example 1         47    Cl NH                                                                                     ##STR87##       262-3 decomposition                                                                      analogously to Example 1         48    Cl                                                                                ##STR88##                                                                             ##STR89##       Oil        analogously to Example 1         49    Cl NH                                                                                     ##STR90##       180-1 decomposition                                                                      analogously to Example 1         50    Cl NH                                                                                     ##STR91##       208 decomposition                                                                        analogously to Example 1         51    Cl NH                                                                                     ##STR92##       191-2 decomposition                                                                      see Example 1                    52    Cl O                                                                                      ##STR93##        96 (Petroleum ether)                                                                    see Example 2                    53    Cl O                                                                                      ##STR94##        83-4      analogously to Example 2         54    Cl O                                                                                      ##STR95##        94-6      analogously to Example 2         55    Cl O                                                                                      ##STR96##       107-8      analogously to Example 2         56    Cl S                                                                                      ##STR97##        87-9      analogously to Example 2         57    Cl S                                                                                      ##STR98##        83-5      analogously to Example 2         58    Cl S                                                                                      ##STR99##        93        analogously to Example 2         59    Cl                                                                                ##STR100##                                                                            ##STR101##       94 (Cyclohexane)                                                                        analogously to Example 2         60    Cl                                                                                ##STR102##                                                                            ##STR103##      240 decomposition                                                                        analogously to Example 2         61    Cl NH                                                                                     ##STR104##      178-9 decomposition                                                                      analogously to Example 1         62    Cl NH                                                                                     ##STR105##      >260       analogously to Example 1         63    Cl NH                                                                                     ##STR106##      108 (Cyclohexane)                                                                        analogously to Example 4         64    Cl S                                                                                      ##STR107##       62-5      analogously to Example 2         65    Cl                                                                                ##STR108##                                                                           CH.sub.3         182.5      analogously to Example 3         66    Cl SO.sub.2                                                                               ##STR109##      153-153.5 (Cyclohexane)                                                                  see Examples 12 and 13           67    Cl                                                                                ##STR110##              138-9 (Toluene)                                                                          see Example 10                   68    Cl NH      CH.sub.3         212 (Z.)   see Example 11                                                     (Methanol)                                  69    Cl NH                                                                                     ##STR111##      186-7 decomposition                                                                      analogously to Example 1         70    Cl NH                                                                                     ##STR112##      214-5 decomposition                                                                      analogously to Example 1         71    Cl NH                                                                                     ##STR113##      167-9 decomposition                                                                      analogously to Example 1         72    Cl NH                                                                                     ##STR114##      153-4 decomposition                                                                      analogously to Example 1         73    Cl SO                                                                                     ##STR115##      112        see Example 14                   74    Cl NH                                                                                     ##STR116##      208-9 decomposition                                                                      analogously to Example 1         75    Cl O                                                                                      ##STR117##       87-8      analogously to Example 2         76    Cl O                                                                                      ##STR118##      103-4      analogously to Example 2         77    Cl O                                                                                      ##STR119##       79-80     analogously to Example 2         78    Cl O                                                                                      ##STR120##       43        analogously to Example 2         79    Cl O                                                                                      ##STR121##      106-7      analogously to Example 2         80    Cl O                                                                                      ##STR122##      Oil        analogously to Example 2         81    Cl O                                                                                      ##STR123##      147-8      analogously to Example 2         82    Cl O                                                                                      ##STR124##       44-5      analogously to Example 2         83    Cl O                                                                                      ##STR125##       76-7      analogously to Example 2         84    Cl S                                                                                      ##STR126##      Oil        analogously to Example 2         85    Cl O                                                                                      ##STR127##       54        analogously to Example 2         86    Cl O                                                                                      ##STR128##       98        analogously to Example 2         87    Cl O                                                                                      ##STR129##      188-9      analogously to Example 2         88    Cl NH                                                                                     ##STR130##       48-9      analogously to Example 1         89    Cl O                                                                                      ##STR131##       96        analogously to Example 2         90    Cl O                                                                                      ##STR132##       51-2      analogously to Example 2         91    Cl O                                                                                      ##STR133##       45        analogously to Example 2         92    Cl O                                                                                      ##STR134##      Oil        analogously to Example 2         93    Cl O                                                                                      ##STR135##       57        analogously to Example 2         94    Cl O                                                                                      ##STR136##       61        analogously to Example 2         95    Cl NH                                                                                     ##STR137##      191-2      analogously to Example 1         96    Cl NH                                                                                     ##STR138##      203        analogously to Example 1         97    Cl NH                                                                                     ##STR139##      226-7 decomposition                                                                      analogously to Example 1         98    Cl NH                                                                                     ##STR140##      124-5 decomposition                                                                      analogously to Example 1         99    Cl NH                                                                                     ##STR141##      157-8 decomposition                                                                      analogously to Example 1         100   Cl NH                                                                                     ##STR142##      112-3 decomposition                                                                      analogously to Example 1         101   Cl NH                                                                                     ##STR143##       77-8      analogously to Example 1         102   Cl NH                                                                                     ##STR144##      158-9 decomposition                                                                      analogously to Example 1         103   Cl NH                                                                                     ##STR145##      163-4 decomposition                                                                      analogously to Example 1         104   Cl O                                                                                      ##STR146##      128        analogously to Example 2         105   Cl O                                                                                      ##STR147##      187        analogously to Example 2         106   Cl S                                                                                      ##STR148##      Oil        analogously to Example 15        107   Cl S       C(CH.sub.3).sub.3                                                                              Oil        see Example 15                   108   Cl S                                                                                      ##STR149##       95        analogously to Example 2         - -109                                                                              Cl O                                                                                      ##STR150##       56        analogously to Example 2         110   Cl O                                                                                      ##STR151##       67        analogously to Example 2         111   I                                                                                 ##STR152##                                                                            ##STR153##       86-8 decomposition                                                                      analogously to Example 2                                                      from 2-Chloro-4-iodo-                                                         5-nitrothiazole                  112   Br                                                                                ##STR154##                                                                            ##STR155##      102-4 decomposition                                                                      analogously to Example 1         113   Cl                                                                                ##STR156##                                                                           CH.sub.2CHCH.sub.2                                                                             130        analogously to Example 1         114   Cl                                                                                ##STR157##                                                                            ##STR158##      141 (Petroleum ether)                                                                    in Tetrahydrofuran with                                                       addition of sodium hydride       115   Cl                                                                                ##STR159##                                                                           CH.sub.2CHCH.sub.2                                                                             Oil        analogously to Example 1         116   Cl                                                                                ##STR160##                                                                            ##STR161##      121-2      analogously to Example 1         117   Cl                                                                                ##STR162##                                                                            ##STR163##      157-8 decomposition                                                                      analogously to Example 1         118   Cl                                                                                ##STR164##                                                                            ##STR165##      169-70 decomposition                                                                     analogously to Example 1         119   Cl                                                                                ##STR166##                                                                            ##STR167##       71-2 decomposition                                                                      analogously to Example 2         120   Cl                                                                                ##STR168##                                                                            ##STR169##      259 decomposition                                                                        analogously to Example 1         121   Cl                                                                                ##STR170##                                                                            ##STR171##      262-3 decomposition                                                                      analogously to Example 1         122   Cl                                                                                ##STR172##                                                                            ##STR173##      >280       analogously to Example 1         123   Cl                                                                                ##STR174##                                                                            ##STR175##      266-7 decomposition                                                                      analogously to Example 1         124   Cl                                                                                ##STR176##                                                                            ##STR177##      202-3 decomposition                                                                      analogously to Example 1         125   Cl                                                                                ##STR178##                                                                            ##STR179##      127-8      analogously to Example 1         126   Cl                                                                                ##STR180##                                                                           CH.sub.2CH.sub.2CN                                                                             176 decomposition                                                                        analogously to Example 1         127   Cl                                                                                ##STR181##                                                                            ##STR182##      154-5 decomposition                                                                      analogously to Example 1         128   Cl                                                                                ##STR183##                                                                            ##STR184##       161-2 decomposition                                                                     analogously to Example 1         129   Cl O                                                                                      ##STR185##      124-5      analogously to Example 2         130   Cl O                                                                                      ##STR186##      111-2      analogously to Example 2         131   Cl                                                                                ##STR187##                                                                            ##STR188##      185-6 decomposition                                                                      analogously to Example 1         132   Cl                                                                                ##STR189##                                                                            ##STR190##      174-5 decomposition                                                                      analogously to Example 1         133   Cl                                                                                ##STR191##                                                                            ##STR192##      268-9 decomposition                                                                      analogously to Example 1         134   Cl                                                                                ##STR193##                                                                            ##STR194##      189-90 decomposition                                                                     analogously to Example 1         135   Cl O                                                                                      ##STR195##       80        analogously to Example 2         136   Cl                                                                                ##STR196##                                                                            ##STR197##      151-2 decomposition                                                                      analogously to Example 1         137   Cl                                                                                ##STR198##                                                                            ##STR199##      165-6 decomposition                                                                      analogously to Example 1         138   Cl                                                                                ##STR200##                                                                            ##STR201##      226-7 decomposition                                                                      analogously to Example 1         139   Cl                                                                                ##STR202##                                                                            ##STR203##      157-8 decomposition                                                                      analogously to Example 1         140   Cl S                                                                                      ##STR204##      154-5 decomposition (Acetonitrile)                                                       analogously to Example 2         141   Cl                                                                                ##STR205##                                                                            ##STR206##      Oil        analogously to Example 1         142   Cl S                                                                                      ##STR207##       95        analogously to Example 2         143   Cl S                                                                                      ##STR208##       52-3      analogously to Example 2         144   Cl S                                                                                      ##STR209##       80-1      analogously to Example 2         145   Cl O                                                                                      ##STR210##      123-4      analogously to Example 2         146   Cl O                                                                                      ##STR211##      134-5      analogously to Example 2         147   Cl O                                                                                      ##STR212##       75-6      analogously to Example 2         148   Cl S                                                                                      ##STR213##      117-8      analogously to Example 2         149   Cl S                                                                                      ##STR214##       96-97     analogously to Example 2         150   Cl O                                                                                      ##STR215##      Oil        analogously to Example 2         151   Cl O                                                                                      ##STR216##       57        analogously to Example 2         152   Cl O                                                                                      ##STR217##       58-9      analogously to Example 2         153   Cl O                                                                                      ##STR218##      208-9      analogously to Example 2         154   Cl O                                                                                      ##STR219##      Oil        analogously to Example 2         155   Cl O                                                                                      ##STR220##       98        analogously to Example 2         156   Cl O                                                                                      ##STR221##       83        analogously to Example 2         157   Cl O                                                                                      ##STR222##       96        analogously to Example 2         158   Cl NH                                                                                     ##STR223##      106-7 decomposition                                                                      analogously to Example 1         159   Cl O                                                                                      ##STR224##      Oil        analogously to Example 2         160   Cl O                                                                                      ##STR225##       97        analogously to Example 2         161   Cl O                                                                                      ##STR226##      106        analogously to Example 2         162   Cl O                                                                                      ##STR227##      116        analogously to Example 2         163   Cl O                                                                                      ##STR228##      Oil        analogously to Example 2         164   Cl  O                                                                                     ##STR229##       68        analogously to Example 2         165   Cl O                                                                                      ##STR230##       78        analogously to Example 2         166   Cl O                                                                                      ##STR231##       68        analogously to Example 2         167   Cl O                                                                                      ##STR232##      115        analogously to Example 2         168   Cl O                                                                                      ##STR233##      152        analogously to Example 2         169   Cl O                                                                                      ##STR234##       86        analogously to Example 2         170   Cl O                                                                                      ##STR235##      Oil        analogously to Example 2         171   Cl O                                                                                      ##STR236##      Oil        analogously to Example 2         172   Cl O                                                                                      ##STR237##      Oil        analogously to Example 2         173   Cl O                                                                                      ##STR238##       52        analogously to Example 2         174   Cl SO.sub.2                                                                               ##STR239##      125 decomposition                                                                        analogously to Example 13        175   Cl O                                                                                      ##STR240##      Oil        analogously to Example 2         176   Cl O                                                                                      ##STR241##      122        analogously to Example 2         177   Cl O                                                                                      ##STR242##      113        analogously to Example 2         178   Cl O                                                                                      ##STR243##       86        analogously to Example 2         179   Cl O                                                                                      ##STR244##      Oil        analogously to Example 2         180   Cl                                                                                ##STR245##                                                                            ##STR246##      144 decomposition                                                                        analogously to Example 1         181   Cl                                                                                ##STR247##                                                                            ##STR248##      162-3 decomposition                                                                      analogously to Example 1         182   Cl                                                                                ##STR249##                                                                            ##STR250##      148 decomposition                                                                        analogously to Example 1         183   Cl                                                                                ##STR251##                                                                            ##STR252##      201-2 decomposition                                                                      analogously to Example 1         184   Cl                                                                                ##STR253##                                                                            ##STR254##      205-6 decomposition                                                                      analogously to Example 1         185   Cl                                                                                ##STR255##                                                                            ##STR256##      168-9 decomposition                                                                      analogously to Example 1         186   Cl                                                                                ##STR257##                                                                            ##STR258##      126 decomposition                                                                        analogously to Example 1         187   Cl                                                                                ##STR259##                                                                            ##STR260##      117 decomposition                                                                        analogously to Example 1         188   Cl                                                                                ##STR261##                                                                            ##STR262##      140-1 decomposition                                                                      analogously to Example 1         189   Cl                                                                                ##STR263##                                                                            ##STR264##      126-7 decomposition                                                                      analogously to Example 1         190   Cl                                                                                ##STR265##                                                                            ##STR266##      179-80 decomposition                                                                     analogously to Example 1         191   Cl                                                                                ##STR267##                                                                            ##STR268##      Oil        analogously to Example 1         192   Cl                                                                                ##STR269##                                                                            ##STR270##      221 decomposition                                                                        analogously to Example 1         193   Cl                                                                                ##STR271##                                                                            ##STR272##      177-8 decomposition                                                                      analogously to Example 1         194   Cl                                                                                ##STR273##                                                                            ##STR274##      201 decomposition                                                                        analogously to Example 1         195   Cl                                                                                ##STR275##                                                                            ##STR276##       94-5      analogously to Example 1         196   Cl                                                                                ##STR277##                                                                            ##STR278##       87-8      analogously to Example 1         197   Cl                                                                                ##STR279##                                                                            ##STR280##       71        analogously to Example 1         198   Cl                                                                                ##STR281##                                                                            ##STR282##      141 decomposition                                                                        analogously to Example 1         199   Cl                                                                                ##STR283##                                                                            ##STR284##      144 decomposition                                                                        analogously to Example 1         200   Cl                                                                                ##STR285##                                                                            ##STR286##       97-8 decomposition                                                                      analogously to Example 1         201   Cl                                                                                ##STR287##                                                                            ##STR288##      161-2 decomposition                                                                      analogously to Example 1         202   Cl                                                                                ##STR289##                                                                            ##STR290##      224-5 decomposition                                                                      analogously to Example 1         203   Cl                                                                                ##STR291##                                                                            ##STR292##      159-60 decomposition                                                                     analogously to Example 1         204   Cl                                                                                ##STR293##                                                                            ##STR294##      204-5 decomposition                                                                      analogously to Example 1         -205  Cl                                                                                ##STR295##                                                                            ##STR296##      213-4 decomposition                                                                      analogously to Example 1         206   Cl                                                                                ##STR297##                                                                            ##STR298##      161-2 decomposition                                                                      analogously to Example 1         207   Cl                                                                                ##STR299##                                                                            ##STR300##      209 decomposition                                                                        analogously to Example 1         208   Cl                                                                                ##STR301##              162-3 decomposition                                                                      analogously to Example 3         209   Cl                                                                                ##STR302##               91-2      analogously to Example 3         210   Cl                                                                                ##STR303##              113 decomposition                                                                        analogously to Example 3         211   Cl                                                                                ##STR304##                                                                            ##STR305##      167-8 decomposition                                                                      analogously to Example 1         212   Cl                                                                                ##STR306##                                                                            ##STR307##      256 decomposition                                                                        analogously to Example 1         213   Cl                                                                                ##STR308##                                                                            ##STR309##       83        analogously to Example 1         214   Cl                                                                                ##STR310##                                                                            ##STR311##      112-3      analogously to Example 1         215   Cl                                                                                ##STR312##                                                                            ##STR313##      254 decomposition                                                                        analogously to Example 1         216   Cl                                                                                ##STR314##                                                                            ##STR315##      Oil        analogously to Example 1         217   Cl                                                                                ##STR316##                                                                            ##STR317##      221 decomposition                                                                        analogously to Example 1         218   Cl                                                                                ##STR318##                                                                            ##STR319##      228 decomposition                                                                        analogously to Example 1         219   Cl                                                                                ##STR320##                                                                            ##STR321##      168-9 decomposition                                                                      analogously to Example 1         220   Cl                                                                                ##STR322##                                                                            ##STR323##      117-8 decomposition                                                                      analogously to Example 1         221   Cl                                                                                ##STR324##                                                                            ##STR325##      156-7 decomposition                                                                      analogously to Example 1         222   Cl                                                                                ##STR326##                                                                            ##STR327##      202 decomposition                                                                        analogously to Example 1         223   Cl                                                                                ##STR328##                                                                            ##STR329##      186-7 decomposition                                                                      analogously to Example 1         224   Cl                                                                                ##STR330##                                                                            ##STR331##      163-4 decomposition                                                                      analogously to Example 1         225   Cl                                                                                ##STR332##                                                                            ##STR333##      156-7 decomposition                                                                      analogously to Example 1         226   Cl                                                                                ##STR334##                                                                            ##STR335##      148-9 decomposition                                                                      analogously to Example 1         227   Cl                                                                                ##STR336##                                                                            ##STR337##      230 decomposition                                                                        analogously to Example 1         228   Cl                                                                                ##STR338##                                                                            ##STR339##      159-60 decomposition                                                                     analogously to Example 1         229   Cl O                                                                                      ##STR340##      247        analogously to Example 2         230   Cl                                                                                ##STR341##                                                                            ##STR342##      198-9 decomposition                                                                      analogously to Example 1         231   Cl                                                                                ##STR343##                                                                            ##STR344##      149-50 decomposition                                                                     analogously to Example 1         232   Cl                                                                                ##STR345##                                                                           C.sub.2 H.sub.5  167-8 decomposition                                                                      analogously to Example 11        233   Cl                                                                                ##STR346##                                                                           CH.sub.2C.sub.2 H.sub.5                                                                        106 decomposition                                                                        analogously to Example 11        234   Cl                                                                                ##STR347##                                                                            ##STR348##      125-7 decomposition                                                                      analogously to Example 11        235   Cl                                                                                ##STR349##                                                                           CH.sub.2CH.sub.2OCH.sub.3                                                                      124-8      analogously to Example 11        236   Cl                                                                                ##STR350##                                                                           CH.sub.2CH.sub.2Cl                                                                             143-4 decomposition                                                                      analogously to Example 11        237   Cl S                                                                                      ##STR351##       97-8 decomposition                                                                      analogously to Example 2         238   Cl O                                                                                      ##STR352##      136-7      analogously to Example 2         239   Cl O                                                                                      ##STR353##      186-7 decomposition                                                                      analogously to Example 2         240   Cl O                                                                                      ##STR354##       82        analogously to Example 2         241   Cl O                                                                                      ##STR355##      142        analogously to Example 2         242   Cl O                                                                                      ##STR356##      103-4      analogously to Example 2         243   Cl O                                                                                      ##STR357##       71        analogously to Example 2         244   Cl O                                                                                      ##STR358##       48        analogously to Example 2         245   Cl O                                                                                      ##STR359##       77        analogously to Example 2         246   Cl O                                                                                      ##STR360##      Oil        analogously to Example 2         247   Cl O                                                                                      ##STR361##      142 decomposition                                                                        analogously to Example 2         248   Cl O                                                                                      ##STR362##      108        analogously to Example 2         249   Cl O                                                                                      ##STR363##      102-3      analogously to Example 2         250   Cl O                                                                                      ##STR364##      104        analogously to Example 2         251   Cl O                                                                                      ##STR365##      159        analogously to Example 2         252   Cl O                                                                                      ##STR366##      145        analogously to Example 2         253   Cl O                                                                                      ##STR367##      112        analogously to Example 2         254   Cl O                                                                                      ##STR368##      102        analogously to Example 2         255   Cl O                                                                                      ##STR369##      141        analogously to Example 2         256   Cl O                                                                                      ##STR370##      104        analogously to Example 2         257   Cl O                                                                                      ##STR371##      101        analogously to Example 2         258   Cl O                                                                                      ##STR372##      137        analogously to Example 2         259   Cl O                                                                                      ##STR373##      129-30     analogously to Example 2         260   Cl O                                                                                      ##STR374##      149        analogously to Example 2         261   Cl O                                                                                      ##STR375##      128-9      analogously to Example           __________________________________________________________________________                                                 2                            

USE EXAMPLES

The compounds shown below were employed as comparison substances in theuse examples which follow: ##STR376##N-trichloromethylthio-tetrahydrophthalimide (compare U.S. Pat. No.2,553,770); ##STR377##N,N-dimethyl-N'-phenyl-N'-(flourodichloromethylyhio)sulphamide (compareDAS (German Published Specification) 1,193,498) on ##STR378##2-cyano-N-(ethylaminocarbonyl)-2-methoximino) -acetamide (compare U.S.Pat. No. 3,957,847) or ##STR379## 4-benzimidazol-2-yl-thiazole (compareR. Wegler "Chemmie der Planzenschutz-und Schadlingsbekam pfungsmittel"(Chemical of Plant Protection Agents and Pesticides), Vol. 2, page 124,Springer-Verlag, Berlin, Heidelberg, N.Y. 1970),

EXAMPLE A Venturia test (apple)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous conidiasuspension of the apple scab causative organism (Venturia inaequalis)and then remain in an incubation cabin at 20° C. and 100% relativeatmospheric humidity for 1 day.

The plants are then placed in a greenhouse at 20° C. and a relativeatmospheric humidity of about 70%.

Evaluation is carried out 12 days after the inoculation.

At an active compound concentration of, for example, 5 ppm, many of thecompounds according to the invention exhibit a degree of action ofbetween 80 and 85% in comparison with the untreated control.

EXAMPLE B Plasmopara test (vines)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Plasmopara viticola and then remain in a humidity chamberat 20° to 22° C. and 100% relative atmospheric humidity for 1 day. Theplants are then placed in a greenhouse at 22° C. and about 80%atmospheric humidity for 5 days. The plants are then moistened andplaced in a humidity chamber for 1 day.

Evaluation is carried out 7 days after the innoculation.

Many of the compounds according to the invention exhibit a degree ofaction of between 80 and 95% in comparison with the untreated control atan active compound concentration of 10 ppm.

EXAMPLE C Phytophthora test (tomato)/protective

Solvent: 4.7 parts by weight of acetone

Emulsifier: 0.3 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dripping wet. After the spraycoating has dried on, the plants are inoculated with an aqueous sporesuspension of Phytophthora infestans.

The plants are placed in an incubation cabin at 100% relativeatmospheric humidity and at about 20° C.

Evaluation is carried out 3 days after the inoculation.

At an active compound concentration of 10 ppm, many of the compoundsaccording to the invention exhibit a degree of action of between 80 and95% in comparison with the untreated control.

EXAMPLE D Leptosphaeria nodorum test (wheat)/protective

Solvent: 100 parts by weight of dimethylformamide

Emulsifier: 0.25 part by weight of alkylaryl polyglycol ether.

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with water to the desiredconcentration.

To test for protective activity, young plants are sprayed with thepreparation of active compound until dew-moist. After the spray coatinghas dried on, the plants are sprayed with a conidia suspension ofLeptosphaeria nodorum. The plants remain for 48 hours in an incubationcabin at 20° C. and 100% relative atmospheric humidity.

The plants are placed in a greenhouse at a temperature of about 15° C.and a relative atmospheric humidity of about 80%.

Evaluation is effected 10 days after the inoculation.

At 0.025% by weight in the spray liquor, some of the compounds accordingto the invention exhibit a degree of action of 100% in comparison withthe untreated control.

EXAMPLE E

In order to determine the activity against fungi on industrialmaterials, the minimum inhibitory concentrations (MIC) of activecompounds according to the invention are determined:

An agar prepared from beerwort and peptone is treated with activecompounds according to the invention at concentrations of from 0.1 mg/lto 5,000 mg/l. After solidification, the agar is contaminated with purecultures of the test organisms listed in the table. After storage for 2weeks at 28° C. and a relative atmospheric humidity of 60 to 70%, theMIC is determined. The MIC is the lowest concentration of activecompound at which no infestation by the microbe species used takesplace.

Thus, for example, compound Nos. 3, 6, 7, 9, 11, 45, 52, 53, 54, 55, 56,64, 80, 77, 78 and 92 and also Examples A1 and A2 have a good action anda broad range of action in the case, for example, of the following testorganisms:

Alternaria tenuis

Aspergillus niger

Aureobasidium pullulans

Chaetomium globosum

Cladosporium cladosporioides

Lentinus tigrinus

Penicillium glaucum

Sclerophoma pityophila

Trichhoderma viride

EXAMPLE F Action against bacteria on industrial materials

An agar containing broth as the nutrient medium is treated with activecompounds according to the invention at concentrations of from 1 to5,000 ppm. The nutrient medium is then infected with each of the testorganisms listed in the table given below, and the infected medium iskept for 2 weeks at 28° C. and a relative atmospheric humidity of 60 to70%. The MIC is the lowest concentration of active compound at which noinfestation by the microbe species used takes place.

                  TABLE                                                           ______________________________________                                                  Escherichia coli                                                              Staphylococcus aureus                                               ______________________________________                                    

In the case of these test organisms, the compounds 3, 6, 9, 53, 77, 78and Examples A1 and A2, for example, exhibit a clearly superior actionthan the known comparative substance (D).

EXAMPLE G

A mixed culture of blue-green, brown and silicious algae (Stichococcusbacillaris Naegeli, Euglena gracilis Klebs, Chlorella pyrenoidosa Chick,Phormidium foveolarum Gomont, Oscillatoria geminata Meneghini and Phaeodactylum tricornutum Bohlin) is introduced into Allen's nutrientsolution (Arch. Mikrobiol. 17, 34 to 15 (1952)) containing 0.2 g ofammonium chloride, 4.0 g of sodium nitrate, 1.0 g of dipotassiumhydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesiumsulphate and 0.02 g of iron chloride per 4 l of sterile water, while airis bubbled through. After 2 weeks, the nutrient solution has become anintense green-blue color due to intensive algal growth. The dieing-offof the algae after active compounds according to the invention have beenadded can be seen from decoloration of the nutrient solution. Thus, forexample, Examples A1 and A2 have a good action.

TABLE H Action against slime organisms

Compounds according to the invention are used, dissolved in a littleacetone, in concentrations of, in each case, 0.1 to 100 mg/l in Allen'snutrient solution (Arch. Mikrobiol. 17, 34 to 53 (1952) containing 0.2 gof ammonium chloride, 4.0 g of sodium nitrate, 1.0 g of dipotassiumhydrogen phosphate, 0.2 g of calcium chloride, 2.05 g of magnesiumsulphate, 0.02 g of iron chloride and 1% of caprolactam in 4 1 ofsterile water. Shortly beforehand, the nutrient solution is infectedwith slime organisms (about 10⁶ organisms/ml) isolated from spinningwater circuits used in the production of nylon. Nutrient solutionshaving the minimum inhibitory concentration (MIC) or greater activecompound concentrations are still completely clear after culturing for 3weeks at room temperature, i.e. notable degrees of multiplication of themicrobes and slime formation do not occur in the active compound-freenutrient solutions after 3 to 4 days.

Thus, for example, the compound of Example A2 exhibits a very goodaction.

It will be appreciated that the instant specification and claims are setforth by way of illustration and not limitation, and that variousmodifications and changes may be made without departing from the spiritand scope of the present invention.

What is claimed is:
 1. A 4-halogeno-5-nitrothiazole of the formula##STR380## in which Hal represents halogen,A represents O, S, SO or SO₂,and R represents alkyl, alkenyl or alkinyl, it being possible for theabovementioned radicals in each case to be optionally substituted by oneor more identical or different substituents from the group consisting ofhalogen, alkoxy, aryloxy, alkylmercapto, arylmercapto and cyano, orrepresents cycloalkyl which optionally carries a fused-on ring and whichis optionally substituted by one or more identical or different alkylsubstituents, or represents aralkyl which is optionally substituted inthe aryl part by one or more identical or different substituents fromthe group consisting of halogen, alkyl, halogenoalkyl, nitro, alkoxy,alkylmercapto and cyano, or represents aryl which is optionallysubstituted by one or more identical or different substituents from thegroup consisting of halogen, alkyl, alkenyl, alkinyl, halogenoalkyl,nitro, alkoxy, alkylmercapto, dialkylamino, carbalkoxy, carbamoyl,N-alkylcarbamoyl, N,N-dialkylcarbamoyl, halogenoalkyloxy,halogenoalkylmercapto, alkylsulphonylamino; alkylsulphonyl, aryl,aryloxy, arylmercapto, acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl,N,N-dialkylsulphamoyl, aralkyloxy, aralkylmercapto, acylamino,acylalkylamino, cyclo-alkyl and cyano, the alkyl radicals having 1 to 12carbon atoms, the alkenyl radicals having 3 to 12 carbon atoms, thealkinyl radicals having 4 to 12 carbon atoms, the cycloalkyl radicalshaving 3 to 8 carbon atoms, the aryl radicals having 6 to 12 carbonatoms, and the aralkyl radicals having 7 to 16 carbon atoms.
 2. A4-halogeno-5-nitrothiazole according to claim 1, in whichA--R representsOR, wherein R represents alkyl, alkenyl or alkinyl, or representscycloalkyl which optionally carries a fused-on ring and which isoptionally substituted by one or more identical or different alkylsubstituents, or for aralkyl which is optionally substituted in the arylpart by one or more identical or different substituents from the groupconsisting of halogen, alkyl, halogenoalkyl, nitro, alkoxy,alkylmercapto and cyano, or for aryl which is optionally substituted byone or more identical or different substituents from the groupconsisting of halogen, alkyl, alkenyl, halogenoalkyl, nitro, alkoxy,alkylmercapto, dialkylamino, carbalkoxy, carbamoyl, N-alkylcarbamoyl,N,N-dialkylcarbamoyl, halogenoalkoxy, halogenoalkylmercapto,alkylsulphonylamino, alkylsulphonyl, aryl, aryloxy, arylmercapto,acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl,aralkyloxy, aralkylmercapto, acylamino, acylalkylamino, cycloalkyl andcyano,or A--R represents SR, wherein R represents alkyl, alkenyl oralkinyl, or represents cycloalkyl which is optionally substituted by oneor more identical or different alkyl substituents, or represents aralkylwhich is optionally substituted in the aryl part by one or moreidentical or different substituents from the group consisting ofhalogen, alkyl, halogenoalkyl, nitro, alkoxy, alkylmercapto and cyano,or represents aryl which is optionally substituted by one or moreidentical or different substituents from the group consisting ofhalogen, alkyl, alkenyl, halogenoalkyl, nitro, alkoxy, alkylmercapto,dialkylamino, carbalkoxy, carbamoyl, N-alkylcarbamoyl,N,N-dialkylcarbamoyl, halogenoalkoxy, halogenoalkylmercapto,alkylsulphonylamino, alkylsulphonyl, aryl, aryloxy, arylmercapto,acyloxy, acyl, sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl,aralkoxy, aralkylmercapto, acylamino, acylalkylamino, cycloalkyl andcyano,or A--R represents SO_(n) R, wherein n represents 1 or 2 and Rrepresents aryl which is optionally substituted by one or more identicalor different substituents from the group consisting of halogen, alkyl,alkenyl, halogenoalkyl, nitro, alkoxy, alkylmercapto, dialkylamino,carbalkoxy, carbamoyl, N-alkylcarbamoyl, N,N-dialkylcarbamoyl,halogenoalkoxy, halogenoalkylmercapto, alkylsulphonylamino,alkylsulphonyl, aryl, aryloxy, arylmercapto, acyloxy, acyl, sulphamoyl,N-alkylsulphamoyl, N,N-dialkylsulphamoyl, aralkyloxy, aralkylmercapto,acylamino, acylalkylamino, cycloalkyl and cyano.
 3. A4-halogeno-5-nitrothiazole according to claim 1, in whichHal representsfluorine, chlorine, bromine or iodine, and R represents alkyl having 1to 12 carbon atoms, alkenyl having 3 to 12 carbon atoms, alkinyl having4 to 12 carbon atoms or halogenoalkyl, halogenoalkenyl orhalogenoalkinyl having in each case up to 8 carbon atoms and 1 to 10identical or different halogen atoms, or represents alkoxyalkyl,alkylmercaptoalkyl or cyanoalkyl having 1 to 4 carbon atoms per alkylpart, or represents phenyloxyalkyl or phenylmercaptoalkyl having 1 to 4carbon atoms in the alkyl part, it being possible for the phenylradicals to be optionally substituted by one to three identical ordifferent substituents from the group consisting of fluorine, chlorine,bromine and alkyl having 1 to 4 carbon atoms, or represents cycloalkylhaving 3 to 8 carbon atoms and optionally substituted by one to threeidentical or different alkyl substituents having 1 to 4 carbon atoms, itbeing possible for the cycloalkyl ring to carry a fused-on ring, orrepresents phenylalkyl having 1 to 4 carbon atoms in the alkyl part andoptionally substituted by one to five identical or differentsubstituents from the group consisting of halogen, alkyl having 1 to 4carbon atoms, halogenoalkyl having 1 to 4 carbon atoms and 1 to 8identical or different halogen atoms, nitro, cyano, alkoxy having 1 to 4carbon atoms and alkylmercapto having 1 to 4 carbon atoms, the alkylpart of the phenylalkyl optionally containing, as a substituent, afurther phenyl radical which can optionally be substituted as describedabove, or represents phenyl which is optionally substituted by one tofive identical or different substituents from the group consisting ofhalogen, nitro, alkyl having 1 to 12 carbon atoms, alkoxy,alkylmercapto, carbalkoxy, alkylsulphonylamino, alkylsulphonyl,sulphamoyl, N-alkylsulphamoyl, N,N-dialkylsulphamoyl, dialkylamino,carbamoyl, N-alkylcarbamoyl or N,N-dialkylcarbamoyl having in each case1 to 4 carbon atoms per alkyl radical, alkenyl or alkinyl having up to 6carbon atoms, halogenoalkyl, halogenoalkoxy or halogenoalkylmercaptohaving in each case 1 to 4 carbon atoms and 1 to 8 identical ordifferent halogen atoms per radical listed, phenyl, phenoxy,phenylmercapto, acyloxy having 1 to 3 carbon atoms, acyl having 1 to 3carbon atoms, phenylalkyloxy having 1 to 3 carbon atoms in the alkylpart, phenylalkylmercapto having 1 to 3 carbon atoms, acylamino having 1to 3 carbon atoms, acylalkylamino having 1 to 3 carbon atoms per acyland alkyl radical, cycloalkyl having 4 to 6 carbon atoms and cyano, orrepresents naphthyl.
 4. A 4-halogeno-5-nitrothiazole according to claim1, in whichHal represents chlorine, bromine or iodine, and R representsalkyl having 1 to 8 carbon atoms, alkenyl having 3 to 8 carbon atoms,alkinyl having 4 to 8 carbon atoms, cycloalkyl having 3 to 6 carbonatoms, cyanoalkyl having 1 to 3 carbon atoms in the alkyl part, orrepresents phenyl, benzyl, phenethyl or naphthyl, optionally substitutedby one to five identical or different substituents from the groupconsisting of alkyl having 1 to 12 carbon atoms, alkenyl having up to 3carbon atoms, fluorine, chlorine, bromine, iodine, trifluoromethyl,nitro, alkoxy having 1 to 4 carbon atoms, alkylmercapto having 1 to 4carbon atoms, dialkylamino having 1 or 2 carbon atoms per alkyl radical,carbalkoxy having 1 or 2 carbon atoms, trifluoromethoxy,trifluoromethylmercapto, alkylsulphonylamino having 1 or 2 carbon atoms,alkylsulphonyl having 1 or 2 carbon atoms, phenyl, phenoxy,phenylmercapto, acetoxy, acetyl, sulphamoyl, N-alkylsulphamoyl having 1or 2 carbon atoms, N,N-dialkylsulphamoyl having 1 or 2 carbon atoms peralkyl radical, carbamoyl, N-alkylcarbamoyl having 1 or 2 carbon atoms,N-N-dialkylcarbamoyl having 1 or 2 carbon atoms per alkyl radicalbenzyloxy, benzylmercapto, formylamino, formylmethylamino, acetylamino,cyclopentyl, cyclohexyl and cyano.
 5. A compound according to claim 1,wherein such compound is 4-chloro-5-nitro-2-(4-methoxyphenoxy)thiazoleof the formula ##STR381##
 6. A compound according to claim 1, whereinsuch compound is 4-chloro-5-nitro-2-(4-nitrophenoxy)-thiazole of theformula ##STR382##
 7. A compound according to claim 1, wherein suchcompound is 4-chloro-5-nitro-2-(4-fluorophenylmercapto)thiazole of theformula ##STR383##
 8. A compound according to claim 1, wherein suchcompound is 4-chloro-5-nitro-2-(2,3-dimethoxyphenoxy)thiazole of theformula ##STR384##
 9. A fungicidal or microbicidal compositioncomprising a fungicidally or microbicidally effective amount of acompound according to claim 1 and a diluent.
 10. A method of combatingfungi or microbes which comprises applying to such fungi or microbes orto a fungus or microbe habitat a fungicidally or microbicidallyeffective amount of a compound according to claim
 1. 11. The methodaccording to claim 10, wherein such compoundis4-chloro-5-nitro-2-(4-methoxyphenoxy)-thiazole,4-chloro-5-nitro-2-(4-nitrophenoxy)-thiazole,4-chloro-5-nitro-2-(4-fluorophenylmercapto)-thiazole, or4-chloro-5-nitro-2-(2,3-dimethoxyphenoxy)-thiazole.